Dhir, Halliday and Sutherland. UK SURVEY OF DIOXINS AND FURANS IN CONSTRUCTION PRODUCTS.

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UK SURVEY OF DIOXINS AND FURANS IN CONSTRUCTION PRODUCTS

(DTI Research Contract No. 39/3/738 cc 2404)
R. K. Dhir, J. E. Halliday, M. A. Sutherland
Produced at the University of Dundee, June 2004 REVISED JUNE 2013
Please note that the references, tables and figures have been scanned. Several industrial organisations, companies and building contractors participated in this project, and some information in the original report cannot be disclosed.
Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.
FOREWORD This report describes work carried out at the University of Dundee, and was confidential during the time of publication. This report was not allowed to be copied, distributed, published, displayed, or referred to in any way without the prior permission of Professor R K Dhir (Director, Concrete Technology Unit (CTU), University of Dundee). NB: Professor Dhir departed from the University of Dundee in 2008. Names of organisations and private companies and individuals who participated in this project (other than the authors) have been withheld.
ACKNOWLEDGEMENTS NB: names of organisations and private companies and individuals who participated in this project (other than the authors) have been withheld.
CONTRIBUTORS TO THE PROJECT (information withheld)
SUMMARY
Dioxins and furans are a family of organic compounds, some of which are classed as human carcinogens. Although these compounds occur naturally, a large proportion is produced unintentionally by the incineration of municipal waste and industries which utilise combustion processes. Approximately 46% of total dioxin and furans released to the environment are from the production of steel; whilst the remainder are from clinical waste incinerators, hazardous waste incinerators, cement kilns and secondary copper smelters, many of which produce materials that are used in construction. Given that many construction materials are derived from thermal processes, it was of immediate importance to gain the confidence of the public, and demonstrate that such materials are not a potential risk to the environment. The approach adopted was be a combination of: (i) carrying out a comprehensive review of the literature available; (ii) obtaining construction materials/products from a number of sites; (iii) developing an analytical procedure to establish the levels of dioxins and furans; and, (iv) disseminating these results. A wide range of housing schemes across the UK were identified and the study was divided into two separate data sets, namely; (a) products used in new construction and (b) products used before 1980. Over 175 samples were obtained from 37 sites across the UK. Gas chromatography/mass spectrometry (GC/MS) is a technique proved suitable for analysing dioxins and furans and is recommended in the EPA 1613 method. The GC/MS instrument represents a device that separates chemical mixtures (the GC component) and a very sensitive detector (the MS component) with a data collector. However, due to the highly sensitive nature of the test (and availability of equipment) it was necessary to develop a new test method using GC and tandem MS/MS. This is a low resolution technique, which uses ion trap spectrometers for the clarification of unknowns, and for analysis of complex mixtures with minimum sample clean up (such as dioxin and furan congeners). Development in the mid-1980s advancing the popularity of MS/MS included the availability of powerful data system able to control the MS/MS experiment. A test method was developed to ensure that each PCDD/F congener was successfully identified and the levels in each sample obtained. In almost all samples, the results showed that there was no peak present at the retention time assigned to a particular congener. However, there were samples tested were a minor peak was detected, therefore indicating that the native dioxin or furan was present. Upon further investigation, through identification of the mass spectra, it was concluded that these particular isotopes were not dioxins or furans. The TEQ value of each sample was calculated as 8.8ng/kg, when detection limits and recovery percentages were taken into consideration.
TABLE OF CONTENTS
LIST OF TABLES LIST OF FIGURES 1: INTRODUCTION 1.1: Background 1.2: Objectives 1.3: Beneficiaries and Expected Impact 2: LITERATURE REVIEW 2.1: Chemistry of Dioxins and Furans 2.2: Formation of Dioxin/Furan Compounds 2.3: Potential Sources 2.4: Potential Exposure 2.5: Dioxin/Furan Levels in the Environment 2.6: Risk Associated with Dioxins/Furans 2.7: EC Directives and National Legislations 2.8: Dioxin/Furan Levels in Materials Suitable for the Construction Industry 3: PROGRAMME OF WORK 4: OBTAINING CONSTRUCTION MATERIALS 4.1: Sampling Strategy 4.2: Samples Collected 5: TEST METHOD 5.1: EPA 1613 Test Procedure 5.2: Gas Chromatography/Mass Spectrometry 6: RESULTS 6.1: Precision and Recovery 6.2: Results 7: CONCLUSIONS REFERENCES 5 5 6-8 6 7 8 9 - 32 9 - 10 10 - 13 13 - 17 18 - 20 20 - 22 22, 23 23 - 25 25 - 33 33 34 34 34 35 - 41 35 - 37 37 - 41 42, 43 42 42, 43 44, 45 46 - 61
LIST OF TABLES (table no., page no.)

1.1 2.1 2.7 2.13 2.19 63 63 67 70 72 2.2 2.8 2.14 2.20 64 67 70 73 2.3 2.9 2.15 2.21 65 68 71 73 2.4 2.10 2.16 2.22 66 68 72 74 2.5 2.11 2.17 2.23 66 69 * * 2.6 2.12 2.18 2.24 67 69 72 75
(None for chapter 3) 4.1 5.1 6.1 6.7 77 77 80 85 5.2 6.2 78 81 5.3 6.3 79 82-84 5.4 6.4 80 84 6.5 85 6.6 85
LIST OF FIGURES (figure no., page no.)

1.1 2.1 2.7 2.13 2.19 3.1 4.1 5.1 5.7 5.13 5.19 5.25 5.31 5.37 86 86 89 93 97 98 99 101 103 107 113 119 125 131 4.2 5.2 5.8 5.14 5.20 5.26 5.32 100 101 104 108 114 120 126 5.3 5.9 5.15 5.21 5.27 5.33 102 104 109 115 121 127 5.4 5.10 5.16 5.22 5.28 5.34 * 105 110 116 122 128 5.5 5.11 5.17 5.23 5.29 5.35 102 105 111 117 123 129 5.6 5.12 5.18 5.24 5.30 5.36 103 106 112 118 124 130 2.2 2.8 2.14 2.20 87 90 94 97 2.3 2.9 2.15 87 90 95 2.4 2.10 2.16 88 91 96 2.5 2.11 2.17 88 92 96 2.6 2.12 2.18 89 92 96
*(omitted)
1: INTRODUCTION
This project has been conceived in response to media coverage and potential public disquiet with respect to the presence of dioxins and furans in construction products, containing waste materials, used in dwellings. The project is hence focused on bringing a more rigorous scientific basis to the question of whether such hazardous materials are present in concentrations sufficient to require further investigation by the relevant Government statutory bodies. As a result of the highly emotive nature of the subject, and the manner in which press and public concerns have been previously aired in the media together with the absence of Independent, reliable data sources - it is considered extremely timely and important to evaluate the compositional nature of relevant construction products.
1.1: Background
Dioxins and Furans Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are two groups of highly toxic organic compounds, which are refractory lipophilic pollutants formed, probably by the interaction of chlorophenols (several other formation theories abound). Dioxins and furans are unintentionally produced by industries that utilise combustion processes and also occur to a lesser extent naturally, for example during forest fires. Although dioxins and furans are present at low levels in the environment, some of them are highly toxic (e.g. 2,3,7,8-TCDD) and are classed as human carcinogens (Brzuzy and Hites, 1996). The main route by which humans are exposed to dioxins and furans is through the digestion of food, with 95% of the daily human intake coming from this source. Dioxins deposited on plants can be taken up by animals and aquatic organisms and, hence, concentrated in the food chain; inhalation and skin contact with contaminated materials accounts for the remainder (EPA, 2001). Research shows that approximately 46% of dioxins and furans generated from combustion processes are released into the environment via the production of steel, but a significant amount are from the incineration of wastes, the production of cement and from secondary copper smelters (EPA, 2001). Many products used in the construction industry either contain raw materials derived from combustion processes, or undergo thermal treatment as part of the manufacturing process. If combustion is incomplete, it is possible that such compounds could potentially be retained and could be released from construction products, such as concrete masonry units, and humans could therefore be at risk. Dioxins and Furans in Construction Products It is widely recognised that any process which involves thermal treatment and/or combustion may produce emissions containing dioxins and furans and may therefore be associated with an end-product containing such compounds (see Table 1.1). Given that
many construction materials are derived from thermal processes and that residues of dioxin/furans may be present, it is important to determine whether such materials present a risk to the occupants of buildings containing them. This project is designed to provide the construction materials industry with data regarding the levels of dioxins and furans present in materials and products acquired from sources throughout the UK and it will give end users of such materials information on the associated risk potential. Risk Routes Figure 1.1 shows an example of the routes dioxins and furans may take during the life cycle of a typical construction product and the potential human exposure mechanisms involved. A previous investigation (BBC Newsnight, 2001) into an isolated construction product containing ash derived from the incineration of municipal solid waste, found that there were unacceptable levels of dioxins and furans. The Government has suggested that dioxin and furan levels should be between 20 and 50ng ITEQ/kg for any material used within the construction industry. It may be added that these limits seem to be based on dioxin and furan concentrations occurring in soils and that, to date, there has not been any formal risk assessment of construction materials/products carried out. The Government's sustainable construction strategy (DOE, 2000) to promote the reuse/recycling of various types of waste, could be undermined if public confidence in commercial products used in construction was aliened by unsubstantiated claims of inclusions of toxic residues. It is therefore imperative that investigations to eliminate any doubt that the public may have and to boost the confidence of end-users in construction products, should be carried out.
1.2: Objectives
The overall aim of the project is to determine the presence and quantities of dioxin and furans in construction materials and products from UK sources. The main objectives of the project were to: (i) collect samples of construction material/products in new dwellings and those older than 1980 from various sites throughout the UK; (ii) to measure dioxin and furan levels in these products; and, (iii) to communicate the results to relevant Government departments/agencies and to provide an input into the discussion on the development of regulatory limits for relevant construction products.
1.3: Beneficiaries and Expected Impact

Economic One of the main beneficiaries of this project will be the construction industry. Through the findings, public confidence in commercial construction products will be reinforced and will allow the manufacture of construction products containing secondary materials from various combustion processes and the recycling of demolition wastes. The repercussions of this would realise an economic benefit for companies within the construction industry. Social As a result of this work, manufacturers of construction products will be able to assess the associated risk with respect to the level of dioxins and furans present, if any, thus giving them the opportunity to strengthen the selling power of such products. Dioxin and furan levels will have a significant effect on the safety of the built environment during construction, service life and decommissioning. By determining that particular building products are environmentally benign, the social benefit to stakeholders in construction will be immense and since many of these products may be used in house construction, it is pertinent to all homeowners. Environmental The end users' confidence in these construction materials will encourage the construction industry to use materials which are currently undervalued. Tins will promote recycling and use of waste materials; a key aim of the Government's sustainable construction strategy. The issue of 'dangerous substances' has been raised at European level under the Construction Products Directive (89/106/EEC). Notwithstanding the development of a database called CREATE, it is acknowledged that quantitative information on known hazardous materials, such as dioxins and furans, is very limited. There is even less information relating to their effects in real dwellings and constructions. This work should add to the data so far and allow rational judgements to be made by appropriate environmental and statutory bodies.
2: LITERATURE REVIEW
The aim of the literature review is to provide a comprehensive overview of the chemistry and formation mechanisms of dioxins and furans, their sources and routes of exposure. In addition, dioxin and furan levels measured in the environment are reported and their potential toxicity and risk to the environment, animals and humans are addressed. The EC directives and national legislations on dioxin and furan emissions are also given and existing literature on levels in construction materials/products summarised.
2.1: Chemistry of Dioxins and Furans

The terms 'dioxin' and 'furan' are usually used to refer to a group of compounds more correctly identified as polychlorinated dibenzodioxins and polychlorinated dibenzofurans. The chemical nature of these compounds is discussed below. Polychlorinated Dibenzodioxins The structures of polychlorinated dibenzodioxins (PCDDs) are based around that of dibenzodioxin (C12O2H8, as shown in Figure 2.1) with one or more chlorine atoms replacing some or all of dibenzo-p-dioxin's hydrogen atoms (Manahan, 1999). This allows for 75 possible compounds (usually referred to as congeners or isomers), which are named by identifying which hydrogen positions are replaced by chlorine. Additionally the names of the compounds also identify the number of chlorine atoms attached to the molecule: the name starts with the term monochloro-, dichloro-, trichloro-, tetrachloro-, pentachloro-, hexachloro-, heptachloro-, and octachloro...for 1, 2, 3, 4, 5, 6, 7, and 8 chlorine atoms, respectively. Examples of PCDD structures are shown in Figure 2.2. PCDDs are solids at room temperature and have high melting points (Williams, 1994). For example, 2,3,7,8 tetrachlorodibenzo-p-dioxin (2,3,7,8 TCDD), for which a great deal of data exists, has a melting point of between 295 and 325 C (Merck & Co, 2001) and is thermally stable up to 700C (Manahan, 1999). They have very low solubility in water; around 0.010.2 g/l for 2,3,7,8 TCDD (Walker, 2001). Solubility decreases with chlorine content. Polychlorinated Dibenzofurans The structures of polychlorinated dibenzofuran (PCDF) molecules are very similar to those of the PCDDs. except that only one oxygen atom is present. The un-chlorinated dibenzofuran molecule around which the other molecules are based is shown in Figure 2.3. The method of naming PCDFs is identical to that of PCDDs. Due to the lower symmetry of the PCDF molecules relative to PCDD, 135 different congeners are possible- The physical properties of PCDFs are comparable to those of PCDDs.
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Toxic Equivalent Factors (TEQs and TEFs) Toxicity varies considerably from compound to compound, with 2,3,7,8 TCDD having the highest toxicity of all, and 2,3,4,7,8-hexachlorodibenzofuran (2,3,4,7,8-PCDF) having the highest toxicity of the furan compounds. Given that analysis of substances contaminated with PCDDs and PCDFs is likely to identify a broad range of dioxin and furan compounds (potentially 210), and that the toxicity of these compounds is the main concern when assessing dioxin levels, it has become standard practice to express the total concentration in terms of TOXIC equivalence (TEQ). TEQ is calculated using the equation (Walker, 2001):
The TEFs for PCDDs and PCDFs were established as a World Health Organisation system in 1994 (Ahlborg et al, 1994) and reassessed in 1998 (van den Berg et al, 1998), based on a previous international system (US EPA, 1989). They express the toxicity of each compound (as best as it is understood) relative to that of 2,3,7,8 TCDD. The factor system also includes polychlorinated biphenyls. The 1989 factor scheme is shown in Table 2.1.
2.2: Formation of Dioxin/Furan Compounds

The formation of PCDDs and PCDFs is generally associated with combustion processes in which chlorine is present. Lustenhouwer et al (1980) proposed three mechanisms by which PCDDs and PCDFs are formed: (1): it is proposed that some PCDDs and PCDFs will already be present in fuels and other materials involved in the combustion process, and will survive the combustion process due to their thermal stability. However, studies which have compared quantities of dioxins and furans entering and leaving combustion processes have all concluded that a higher mass of the compounds exit the process, meaning that synthesis of additional compounds certainly occurs during or after combustion (Hay et al, 1986; Commoner et al, 1987; Clement et al, 1988). It has also been demonstrated that 99.95% by mass of dioxins and furans are destroyed at 500 C (Stehl and Lamparski, 1977), meaning that the temperatures of a combustion process must be reasonably low to permit PCDDs and PCDFs to pass through unharmed.
(2): PCDDs and PCDFs may be formed from structurally related precursor molecules present in fuels and other materials. Suggested precursors include polychlorinated biphenyls (PCBs) chlorinated benzenes and chlorinated phenols. An example of one such reaction is shown in
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Figure 2.4. However, more recent research has found that formation from chlorinated benzenes is not favoured (Altwicker et al, 1994). (3): the compounds may be formed via a de novo synthesis route - i.e. entirely from elemental components (carbon, chlorine, hydrogen and oxygen). It is likely that in many combustion scenarios, all of these processes are occurring to some extent. Factors Affecting Dioxin Formation A number of factors influence the extent to which PCDD and PCDF compounds are formed. The major variables identified in the literature are discussed below. Temperature It has been shown that most dioxin formation is likely to occur after combustion, as the exhaust gases cool (Vogg et al, 1987). A number of studies have examined dioxin and furan formation (from precursor compounds, via de novo synthesis, and as a combination of both) over a range of temperatures, allowing optimal temperature ranges to be identified. Table 2.2 shows ranges of temperatures at which PCDD and PCDF formation has been identified to occur, with optimum temperatures identified in some cases. In general, formation occurs at temperatures between 200C and 450C, with variation between the results of different studies probably resulting from differences in other experimental variables. Residual carbon In most combustion processes, fine particles of non-combustible material are often carried away by the exhaust gases. These particulates often carry with them quantities of residual carbon, which appear to Ibrm precursors for PCDD and PCDF formation (Stieglitz et al, 1989). However, more recent research has suggested that it is not the carbon itself, but alkanes and alkenes present in small quantities on the carbon, which decompose during combustion to form phenol precursors (Cains et al, 1997). Chlorine It has been shown thai the formation of PCDDs and PCDFs subsequent to combustion requires that chlorine gas is present (Luijk et al, 1994; Addink et al, 1995). At the point of combustion, most organic chlorine compounds bum to form hydrochloric acid (HCI). It is believed that chlorine gas is formed subsequent lo combustion via a reaction known as the Deacon process (Vogg et al, 1987):
2HCl + O2
H2O + Cl2
Inorganic chloride compounds such as potassium chloride (KCl) and sodium chloride (NaCl) may also be present. These compounds typically volatilize at elevated temperatures, and recondense on particulates as the exhaust gases cool.
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A number of studies have been carried out to determine whether there is a direct relationship between the chlorine content of fuel and other materials involved in the combustion process and PCDD and PCDF output. One study, using a pilot-scale incinerator, monitored the HCl content of exhaust gases (which was used as an inferred measure of fuel chlorine content) along with PCDD and PCDF content (Wagner and Green, 1993). Varying quantities of PVC were also added to the feed to generate a wide range of HCl levels in the exhaust. A clear, positive relationship was identified between HCI levels and PCDD and PCDF emissions. The role of inorganic chloride compounds was addressed by a study in which combinations of PVC and calcium chloride (CaCl2.6H2O) were included in an artificial fuel which was again burnt in a pilot-scale incinerator (Wikstrom et al, 1996). Again, a close correlation was identified between the total chlorine content of the fuel and the quantities of PCDD and PCDF produced. The results also suggested that the form in which the chlorine was present in the fuel (i.e. organic or inorganic) was not important. However, other research suggests that inorganic chloride (at least in the form of NaCI) will only contribute to PCDD and PCDF formation in the absence of organic chlorine-bearing compounds (Addink et al, 1998). Catalysts It is generally agreed that the reactions leading to the formation of PCDDs and PCDFs are promoted by the presence of catalysts present on particulate surfaces in exhaust gases. The catalyst most commonly cited is copper chloride (CuCl2) (Addink and Olie, 1995). Two mechanisms have been proposed for how the compound promotes formation. The first proposed mechanism is that CuCl2 promotes the formation of the aromatic ring structures which act as precursors for PCDD and PCDF formation (Born et al, 1993). The second proposal is that CuCl2 acts as the catalysts to the Deacon process (Vogg et al, 1987). Other compounds which may feasibly be present in particulates derived from combustion have also been shown to promote PCDD and PCDF formation including iron (III) chloride (Nestrick et al, 1987), silica, iron (US) oxide, copper oxide (Froese and Hutzinger, 1996) and alumina (Froese and Hutzinger, 1996). Sulphur The combustion of sulphur-bearing compounds in fuel produces sulphur dioxide (SO2). Whilst this is a substance with its own environmental problems, being one of the major causes of acid rain, it has also been found to be an effective inhibitor of PCDD and PCDF formation. One inhibition mechanism is through the reaction of SO; with the catalysts that are needed for the Deacon process (see above) rendering them ineffective (Froese and Hutzinger, 1996). The other is believed to be a reaction in the gas phase between SO; and chlorine gas (Froese and Hutzinger, 1996):
Cl2 + SO2 + H2O
2HCl + SO2
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However, researchers examining the effect of increasing the amount of sulphur in the fuel used in a fluidized bed combustion boiler found that low additions did have an inhibiting effect on dioxin and furan production (Raghunathan and Gullett, 1996). However, at higher sulphur levels, PCDD and PCDF levels began to increase again. The researchers propose that this may be due to the sulphur additions shifting the equilibrium conditions in the fluidized bed towards a situation mat favours incomplete combustion.
2.3: Potential Sources

Dioxins and furans have always been present in the environment (Constans, 2003). Indeed, traces of dioxin have been found in the bark of woods thousands of years old and in millions of years old clay layers, not influenced by any man-made source (Chlorophiles, 2000). These substances are not manufactured deliberately and the majority (point sources), accounting for about 62% of total dioxin air emissions according to (he European Dioxin Inventory report (cited by EUROPA, 2003), are by-products of industrial processes, mainly thermal treatment/combustion and manufacture of products using chlorine (US Department of Agriculture, Animal and Plant Health Inspection Sources, 2000; EMS, 2003). The remaining 38% of total dioxin air emissions are mainly from non-industrial, more diffuse, sources, including domestic heating facilities (particularly wood combustion), accidental fires and road traffic (Draft document on dioxins, 2000; EnviroTools, 2002; EUROPA, 2003). An example of the wide range of sources of dioxins (PCDD) and furans (PCDF) identified in the United States and their development with time is shown in Figure 2.5. In addition, the most recent record of emissions (g I-TEQ/year) from a range of sources in The UK is reported in Table 2.3, where these are provided with a rating of quality for production and emissions data. As can be seen- in both US and UK sets of data, emissions in waste water appear negligible compared to atmospheric and residual (in landfills or other reservoirs) emissions, which are thought to be within the same order of magnitude (Draft document on dioxins, 2000). Industrial Sources The primary sources of dioxins and furans are industrial processes involving treatment at high temperatures and manufacture of products using compounds containing chlorine. Although the latter was considered to be the main source of dioxins in the past, the reverse has been observed in more recent years (Fiedler et al, 2000). Thermal processes Dioxin (PCDDs) and furan (PCDFs) emissions, predominantly attributed to the combustion of hydrocarbons (Constans, 2003), are closely linked 10 processes earned out at high temperatures, typically above 800C (Environment Australia. 2002). However, the temperature ranges and the stage of the combustion/thermal process during which the emissions occur are unclear. The main industrial thermal processes identified as being responsible for the emissions of PCDDs/Fs include incineration, metal smelters, cement kilns, coal-burning plants etc (Fiedler et al, 2000).
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Incineration Incineration, both municipal and industrial, is the main route by which dioxins and furans are produced (Paddock, 1989). The toxic substances are formed when solid, medical (from hospitals, veterinary practices, crematoria or research facilities), municipal (mainly plastics, PVC; Paddock, 1989; EMS, 2003) or industrial hazardous waste and sewage-sludge are burnt (Draft document on dioxins, 2000; Environment Australia, 2002; Chlorine Chemistry Council, 2003; NRDC, 2001). The incomplete combustion (burnt inefficiently and at low temperatures; Paddock, 1989) of waste in incinerators results in aerial deposition of dioxins (LCREP, 2003), with solid waste incinerators responsible for emitting the highest quantities (WHO, 1999). Although incineration has long been recognised a major source of dioxins and furans, the processes by which these are formed during incineration are not yet completely understood nor agreed upon. The three possibilities proposed by Fiedler et al (2000) and Environment Australia (2002) to explain the presence of dioxins and furans in incinerator emissions are: 1. PCDDs/Fs are already present in the incoming waste ('in-furnace' formation). Indeed, levels of around 50 ng I-TEQ/kg inside fresh waste samples have been measured in some cases. However, these are either completely destroyed or transformed during combustion. PCDD/Fs are produced from related chlorinated precursors/pre-dioxins ('in-furnace' formation). Such substances could be PCB, chlorinated phenols and chlorinated benzenes. It has been proven however, that the quantities of dioxin and furan emissions are not proportional to the amount of chlorine in the incoming waste, as shown schematically in Figure 2.6. PCDDs/Fs are formed from the pyrolysis of chemically unrelated compounds (e.g. PVC or other chlorocarbons) and/or the burning of non-chlorinated organic matter (e.g. polystyrene, cellulose, lignin, coal and particulate carbon) in the presence of chlorine-donors (de novo synthesis). Indeed, PCDD/Fs have been observed when chlorine-containing substances (e.g. PVC residues, chloroparaffins in waste oils and inorganic chlorine) are burnt together with carbon and a suitable catalyst (preferably copper) at temperatures in excess of 300C in the presence of excess air or oxygen. The dioxins are formed when combustion gases cool down from around 450C to 250C (Fiedler et al, 2000).
2.
3.
However, a well-designed and well-run incinerator (mass burn, modular bum or refusederived fuel type) that follows 'good combustion practices', as defined by FPA (US EPA, 1999, cited In Chlorine Chemistry Council, 2003), is expected to destroy dioxins and furans in the waste fuel and minimise their formation during combustion and cooling of incineration gases, hi addition, pollution control devices are available to further reduce emissions (Chlorine Chemistry Council, 2003).
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Other incineration/combustion products which may result in dioxin/furan formation during their manufacture include incineration fly ash. This comprises finely divided panicles round in the flue gases arising from the combustion of waste (Paddock, 19S9). Some research has been carried out in this area and there now exists a reference material for control of the accuracy of test methods and for quality control of the measurement of dioxin and furan levels in fly ash emissions (Rymen, 2003). Metal smelters Various metallurgical processes (ferrous and non-ferrous) carried out in blast furnaces and electric furnaces, including secondary aluminium, steel, copper, nickel, zinc and magnesium smelters, sintering plants and electric furnace steel plants, arc also considered sources of dioxins and furans (Draft document on dioxins, 2000; NRDC, 2001: Environment Australia, 2002; EMS, 2003; Rodan and Cleverly, 2003). More specifically, the most recent estimation of annual PCCD/17 emissions attributed to the production of ferrous materials in (he USA was between 210 and 400 kg TEQ (US Department of Agriculture, Animal and Plant Health Inspection Sources, 2000). Cement and lime manufacture Although cement kilns can be responsible for a proportion of the dioxins and furans in the atmosphere (Draft document on dioxins, 2000), it is recognised that not all are necessarily created by the process. Indeed, some PCDDs/Fs may be present in the kiln raw feed, i.e. when the constituents have a high in hydrocarbon content (Environment Australia, 2002). Additional sources include using contaminated water (e.g. from river) to slurry the wet process kiln teed (Constans, 2003). However, the quantities of PCDD/Fs emitted are up to three orders of magnitude smaller than those in the raw constituents. The US Department of Agriculture, Animal and Plant Health Inspection (2000) have reported that cement kilns burning hazardous and non-hazardous wastes are responsible for (lie emission of between 400 and 960 kg TEQ and between 190 and 450 kg TEQ respectively per year. Given that lime manufacture is very similar to that of cement, it is also responsible for PCDD/F emissions in the atmosphere (Environment Australia, 2002). Other industrial sources of dioxin/furan emissions associated with thermal processes comprise coal- and oil-burning plants (used to generate steam for electricity generation, generate process steam and provide heating), industrial wood combustion (depending on wood waste composition and variability, any co-fired fossil fuels, combustor type and performance and air pollution control systems), glass and ceramic manufacture, incineration of polyvinyl chloride plastic (PVC), wire scrap burning and industrial combustion installations (NRDC, 2001; Environment Australia, 2002). Chemical processes The other significant source of dioxins (PCDDs) and ftirans (PCDFs) is within the chemical industry, more particularly the processes involving manufacture of products using chlorine compounds or chlorine gas, mainly to bleach or disinfect. This used to be responsible for the majority of PCDDs/Fs in the past. However industrial users of chlorine have, in the recent
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years, greatly reduced emissions of dioxins and furans from their production processes and manufacturing facilities (Fiedler et al, 2000; EMS, 2003). Pulp and paper industry Dioxins and furans were discovered in the waste products and discharge? of pulp and paper mills and some paper products and this was linked with the chlorine bleaching process used at some facilities (Paddock, 1989; NRDC, 2001; LCREP, 2003), However, She pulp and paper industry have now virtually eliminated releases of dioxins and furans by using alternative chemicals (e.g. chlorine dioxide) to elemental chlorine in the bleaching processes (Chlorine Chemistry Council, 2003). Polyvinyl chloride plastic - PVC PVC manufacture is also responsible for emissions of dioxins and furans. However, although vinyl production in the US increased from 1bn pounds in 1960 to 11bn pounds in 1995, levels of dioxins and furans in the environment have decreased dramatically during this 35 year period, thereby suggesting that the emissions attributed to PVC manufacture are minimal compared with those from other sources (NRDC, 2001). Chlorophenols The manufacture of a group of chemicals called chlorophenols, mainly by direct chlorination of phenol with chlorine gas or by basic hydrolysis of chlorobenzenes (Environment Australia, 2002) and their by-products, also results in the formation of dioxins and furans. These chemicals are widely used to preserve wood, hides, textiles, paints, glues and other materials, as disinfectants. Pentachlorophenols in particular, used to preserve wood, are known to contain relatively high levels of many of the toxic PCDDs/Fs compounds. As a result, wastes from wood treatment facilities and sawmills are now treated as hazardous, or are proposed to be treated as such (Paddock, 19S9). Cooling fluids Cooling fluids used in electrical equipment and some industrial cooling systems typically comprise polychlorinated biphenyls (PCBs) and other chemicals, both of which are capable of containing low levels of dioxins and furans. Given that a very large amount of PCBs has been released to the environment, these are no longer manufactured in the US and are being removed from most uses (Paddock, 1989). Other industrial sources of dioxin/furan emissions associated with chemical processes include long term storage of waste industrial oils with high levels of dioxins, which are released into the environment and contaminate human and animal food supplies (WHO, 1999). In addition, production of certain herbicides, pesticides, dyes, pigments and electrolytic processes using chlorine can also be responsible for the formation of these substances (NRDC, 2001).
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Non-Industrial Sources Nun-industrial sources of dioxins and furans are of secondary importance and primarily include wood combustion and car emissions (Fiedler et al, 2000). Wood combustion Traces of dioxins and furans have been found in the chimneys of wood- and coal-burning stoves and fireplaces, thereby suggesting that incomplete combustion of wood and coal results in aerial deposition of these substances (Draft document on dioxins, 2000; LCREP, 2003). As a result, it is expected that forest/bush fires, accidental fires, backyard trash burning, cigarettes, illegal domestic combustion and other natural burning (especially if the wood has previously been treated with pentachlorophenols) are responsible for a large amount of the dioxins and furans present in the environment (Paddock, 1989; Draft document on dioxins, 2000; NRDC, 2001; Chlorine Chemistry Council, 2003; EMS, 2003). Car emissions Leaded and diesel fuels, which contain chlorinated additives, produce dioxins and furans when ihey are burned in engines of motor vehicles. As a result, exhaust fumes from road traffic contribute significantly in the aerial deposition of dioxins and furans, especially in urban areas in the US and much of Europe. However, the use of leaded fuel has declined dramatically in the past decade and will continue to decline further (Paddock, 1989; Draft document on dioxins, 2000; NRDC, 2001; Environment Australia, 2002; LCREP, 2003). Natural sources Certain biological processes are sources of dioxins and furans in nature and these explain why, except for 'hot spots', near old incinerators and other point sources, the greatest concentration of dioxins in soil is found in the woods and not in industrial or other areas with heavy traffic. More specifically, wood-rotting fungi and half of all mushrooms use chlorinating and oxidising compounds to break down lignin, a substance which provides strength to all plants. The by-products of these processes comprise chlorinated humic acids and chlorinated lignin in water, chlorinated humus and chlorinated phenols in soil. From chlorinated phenols dioxins can be created with hydrogen peroxide, which is widely produced by many micro-organisms (Chlorophiles, 2000). Other non-industrial sources of dioxins and furans include electrostatic precipitators, oil heating, boilers, explosions, crematoria (both 'cold' and 'warm' types), natural sources (e.g. volcano eruptions), reservoirs (e.g. sewage sludge, compost, liquid manure) and accumulations m harbours, rivers, lakes and oceans due to untreated or insufficiently treated wastes (Draft document on dioxins, 2000; Fiedler et al, 2000; NRDC, 2001; Chlorine Chemistry Council, 2003; EMS, 2003; LCREP, 2003).
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2.4: Potential Exposure

Dioxins and furans are widespread in the environment (LCREP, 2003) and the components of exposure pathways to these chemicals, comprise the source, the transport media (how the contaminants move through the environment), the exposure point (how people come in contact with the contaminants), the exposure route (how the contaminants enter the body) and the receptor population (how susceptible the population is to the contaminants) (Envirotools, 2002). Transport Media As shown schematically in Figure 2.7, dioxin and furan compounds are transported from their sources to distant locations, mainly through atmospheric or aquatic (e.g. groundwater) pathways (Rodan and Cleverly, 2003). Atmospheric pathway The majority of dioxins and furans from both industrial and other sources (e.g. incinerators, metal smelters, cement kilns, wood burning and car emissions) are emitted into the atmosphere (US EPA, cited in GPA, 2000). These are considered to be of the same order of magnitude as the quantities in residues, disposed of in landfill or other reservoirs, and significantly higher those measured in waste water (Draft document on dioxins, 2000). The dioxins and furans are transported on air currents to distant locations around the globe. Indeed, international pollution patterns have indicated some contamination from dioxins and furans even in areas with little industry (NRDC, 2001). Although a small proportion of dioxins and furans in the atmosphere are broken down by sunlight (NRDC, 2001), most gel deposited on the ground or in the water and then get absorbed on particles (e.g. soil or sediment in water), due to their low vapour pressure (Draft document on dioxins, 2000). Aquatic pathway Dioxins and furans created during chemical processes (e.g. from bleaching with chlorine ai pulp and paper mills) are usually discharged with the industrial waste water and thereby introduced to river or sea outlets. Similarly, storm drains and overflows, that discharge urban run-off, can transport dioxins from atmospheric depositions, pesticides and herbicides to river/sea outlets (LCREP, 2003). These accumulate in sediments, together with any untreated or insufficiently treated wastes (NRDC, 2001; LCREP, 2003). Exposure Points Dioxins and furans are widespread in the environment (air, soil, sediments, meat, milk, fish, vegetables) and humans become exposed to them through me ingestion of substances that contain these chemicals, inhalation or dermal contact (Envirotools, 2002; LCREP, 2003).
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Ingestion The principal exposure point of people to these chemicals, accounting for more than 90% of the daily dioxin intake from background contamination, is through dietary exposure. Dioxins and furans have been found in agricultural crops, vegetables, beef, fish, poultry and dairy products (WHO, 1999; GPA, 2000: NRDC, 2001; EMS, 2003; Qua, 2003), For the United States in particular, dioxin intake through food has been estimated around 60 pa TEQ/day (Rodan and Cleverly, 2003), while Fiedler et al (2000) reported that the daily intake attributed to food of animal origin is approximately 2 pg TEQ/kg body weight. The ingestion of water is another point source of dioxins and furans, however, the dose obtained is considerably smaller than that from food (Rodan and Cleverly, 2003). Inhalation People can also become exposed to dioxins and furans by breathing in substances that contain the chemicals (Envirotools, 2002). These can include dioxins and furans in the atmosphere (especially near hazardous waste sites, incinerators), from car emissions, stoves, fireplaces, accidental/forest fires, cigarettes, explosions, and in certain pesticides, herbicides, wood preservatives, paints, glues, textiles all containing chlorophenols (NRDC, 2001). However, the intake of dioxins and furans through inhalation is considered significantly smaller than that obtained through food (Rodan and Cleverly, 2003). Dermal contact Exposure to these contaminants can also occur through direct contact (touching) with substances that contain the chemicals (Envn-oiools, 2002). Such substances may include (as already mentioned above) certain pesticides, herbicides, wood preservatives, paints, glues, textiles, all containing chlorophenols (NRDC, 2001). In addition, skin contact with contaminated water, soil, sediment or incineration products may also be considered of potential risk. Exposure Routes Given that more than 90% of the daily dioxin intake for the general population is attributed to diet (WHO, 1999), the main route of dioxins and furans into the human body is through the food chain (US EPA, cited in GPA, 2000; Rodan and Cleverly, 2003). Food chain Dioxin and furan particles in the atmosphere are transported on air currents and are eventually deposited on the soil, crops or in the water. As a result, a range of food sources get contaminated and these are widely spread in the environment through various physical and biological processes (US EPA, cited in GPA, 2000). Such contaminated food supplies include primarily meat (beef, poultry), dairy products, fish and vegetables (EMS, 2003; GPA, 2000; NRDC, 2001; WHO, 1999).
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Agricultural crops (e.g. vegetables and green feed) become contaminated with dioxins and furan-; mainly from deposition of airborne particles on them, as any direct uptake from contaminated soil into the roots is reported to be of minor significance (Qua, 2003). The chemical substances are then taken up in the food supply by both the human and animal population (Rodan and Cleverly. 2003). Additional quantities of dioxins and furans on crops may result from the use of certain pesticides and herbicides (NRDC, 2001). Live stock and fish are exposed to dioxins and furans through contaminated feed and contamination in the water (river, lake, sea) respectively. Once consumed, these substances are attracted to fat tissues in the living organisms and, as dioxins are resistant to metabolism (NRDC, 2001), they tend to bio-accumulate there and become increasingly concentrated when moving up the food chain from animals to humans (GPA, 2000; EMS, 2003; Rodan and Cleverly, 2003). Dairy products originating from live stock with deposits of dioxins and furans in their tissues have been found to contain Traces of the substances (EMS, 2003; GPA. 2000; NRDC, 2001; WHO, 1999). When the products are consumed by the general population, the contaminants are transferred to human tissues. Other exposure routes Other possible exposure routes of the general population to dioxins and furans, in addition to the food chain, include isolated accidents involving industrial or waste disposal. In addition, residents in areas near hazardous waste sites or incinerators that release dioxins and furans, or workforce in relevant industries that produce dioxin and furan by-products, would be constantly exposed to these chemicals through inhalation and perhaps direct dermal contact (NRDC, 2001), Although some construction materials undergo processes during their manufacture during which dioxins and furans may be produced, only one report exists suggesting that an isolated construction product containing incineration ash from municipal solid waste was found to contain dioxins and furans (BBC Newsnight, 2001).
2.5: Dioxin / Furan Levels in the Environment

Levels of dioxins and furans in the environment have depicted significantly since peaking in the late 1960s and early 1970s (Alcock and Jones, 1996). As shown in Figure 2.8, even though the production of vinyl has increased dramatically over the last 40 years (a once supposed source of dioxin/furan emissions), the levels in food and sediment has deceased. The levels of dioxin/furans in human tissue (such as breast milk, blood and fat), shown in Figure 2.9, have decreased by almost 60% between 1986 and 1996. Stanley et al (1990), Cleverly et al (1996), Haaenmeier and Walzok (1996) and Ferrario et al (1998) all reported that these trends are attributed to improved waste incineration, phase-out of leaded petrol, advances in emissions controls, and prohibitions on open burning, change in pulp and paper bleaching processes and changes in manufacturing processes.
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Air Emissions of dioxins from combustion sources in the atmosphere are determined either directly or as deposition samples. There are three basic approaches to determine these levels: (i) (ii) (iii) high volume samplers which collect particle-bound and gas-phase dioxins; Bergerhoff samplers which collect dry or wet deposition; and, biomonitors (vegetation such as grass, kale and pine- needles).
The UK Department of the Environment, Transport and (he Regions maintains a monitoring network to determine atmospheric concentrations of toxic pollutants (including dioxins and furans). It has been reported that over an eight year period (1990-1998) the total dioxin emissions from both industrial and domestic sources decreased from 1142 to 345 g I-TEQ per year. Table 2.4 gives the results from both rural (three location) and urban (five locations) around the UK for both ambient and deposition. It can be seen that the ambient air results show a distinctive difference between rural and urban areas, with the highest values taken at Stevenage and Cardiff. These higher concentrations may be evidence of time rather than geographical trends. Results for eight European countries were found and it can be seen from results in Table 2.5 that the levels in ambient air have similar trends as those in the UK. Soil The data available for the levels of dioxin/furans in UK soil are dominated by localised surveys, commissioned within areas were contamination is most likely, although it must be noted that a few 'background' surveys have been carried out. It can be seen from results in Table 2.6 that the 'background' levels in soils are between 5-2 and 28 ng I-TEQ/kg and that levels in soil samples from industrial areas (especially near incinerators) can be much higher, although the mean results are very similar with the exception of one location. Figure 2.10 shows the influence of location of the soil sample on levels of dioxins measured. There have been a number of intensive studies carried out within other European countries (as shown in Table 2.7), with almost all countries exhibiting a broad range of dioxin concentrations. It can be concluded that in areas with contaminated land, levels are extremely high (particularly in the Netherlands, Germany and Finland). However, it must be noted that the number of samples taken at a particular location differs from one country to another. River and Lake Sediment The National River Authority (now pan of the Environment Agency) funded a study on the water and sediments in England and Wales (carried out by Rose et al, 1994} and an overview of the results is shown in Table 2.8. It can be seen that agricultural areas seem to have the lowest concentrations, whilst urban catchments exhibit the highest. Rose and McKay carried oul ii separate study on the dioxin levels in lake/loch sediments and it can be seen that
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these were within the same range as those found in rivers. The dioxin levels in sediments in European countries are given in Table 2.9. Sewage Sludge More than 1-2 million tonnes of sewage sludge is generated in the UK each year, and approximately 60% of this is being used in agriculture. Table 2.10 shows the results from a survey earned out for the Department of the Environment, which distinguishes between treatment works from rural and urban catchment areas. It can be seen that the urban treatment plants, which include industrial effluents have a higher concentration of PCDD/PCDF than those from urban plants processing domestic waste and all rural plants. Table 2.10 also shows the levels detected in several other European countries and it is apparent that Germany has an exceptionally high concentration, although the average results are the same as the UK. Vegetation and Food Total Diet Surveys (TDS) are regularly carried out by the Foods Standards Agency to monitor the levels of dioxins/furans in retail foods found throughout the UK. The latest survey data available was carried out in 1997 and it was found that the TEQ values ranged between 0.004 and 8.76 ng TEQ/ kg of fat. Dioxins, which are fat soluble, where generally found in 'fatty' foods, such as fish, meat and milk. Figure 2.11 shows that there is an overall decline in dioxin concentrations in fatty foods in the UK from 1982. Table 2.11 gives the data available for levels in foods in other European countries, and it can be seen that there is a broad range of results depending upon the type of food and the country. Humans Dioxins are known to be ubiquitous in the environment and the entire population has, to some extent, been exposed through contaminated foods, accidental and occupational exposure and through dioxins in the atmosphere. These accumulate in the body and the average concentration increases year by year. The main source of data for the majority of the EU countries was carried out in the periods (1986-1958) and (1992-1993) by the WHO. Table 2.12 gives the average of all reported measurements for those years, for rural, urban and industrial areas, and the percent change over the 5 year dormant period.
2.6: Associated Risks

Risk to the Environment (Ecotoxicology) Dioxin-like chemicals share many physical properties that affect their behaviour in the environment. They dissolve poorly in water, but very well in oils, fats and organic solvents. They adhere to organic compounds such as soil and water and therefore do not 'wash out' easily. They have a low vapour pressure winch means that they do not evaporate readily. Since they do not react with oxygen or water they are not broken down by bacteria (and only very slowly by sunlight) and therefore remain in the environment for a very Song
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period of rime (CHLJ. 1999). Although dioxins are known to absorb into the roots of carrots, pumpkin and zucchini, there has been no information on any detrimental effects these types of vegetation (Schroll, 1993 and Hulster, 1994). Risk to Animals and Humans (Toxicology) Toxicology can be defined as 'the study of harmful effects of chemicals upon biological systems'. It is well documented that PCDD/PCDFs enter the food chain via air, soil, vegetation and then finally humans. Dioxins are not well metabolised in the body thus are not eliminated in urine or faeces. Rather, they dissolve and accumulate in body fat. Most research studies, on the toxicology of dioxins and dioxin-like compounds have been carried out on animals, although there have been a number of studies and reports on the effects of dosages of dioxins/furans on humans. Although studies on animals use prescribed doses under controlled conditions, studies of their effect on health of humans are more complicated as people are more likely to be accidentally exposed to immeasurable doses. Olsen (1994) reported that once in the bloodstream, dioxins stay for a relatively short period of time and then distribute to the fatty tissue around the body. When particularly high doses have been absorbed into the body, a greater proportion is deposited in the liver (Abraham et al, 1988). Elimination of dioxins from the body can occur through the liver and through breast milk, although people with a high percentage of body fat require longer periods of lime for this process to occur (Wolfe et al, 1994). Dioxins and dioxin-like compounds are known to affect the body cells, especially the genetic formation of the chromosomes. The chromosomes are responsible for generating proteins, which in turn make the body work - producing enzymes, hormones, antibodies and a range of other substances. Genes can be turned on or off, depending on the specific function required by the body. Dioxins have the ability to interfere with the genes and disrupt these turning on and off patterns, some of which are critical to normal cell growth. As a result, sometimes genetic mutations or cancer can be caused (Rowlands and Gustafsson. 1997). Several proteins (that influence hormone and growth factors) can be affected, which in turn affect many biochemical and physiological processes, including reproduction and the immune system (Okey et al, 1994) (as shown in Table 2.13). TCDD (dioxin) was declared a probable human carcinogen by the International Agency for Research on Cancer (IARC) in 1997. The dioxin compounds cause many types of cancer in both genders indirectly through various mechanisms. For example, they may weaken the immune system's ability to recognise and destroy cells, increase the risk for the mutation of the protein cells or stimulate the growth of hormone-sensitive cancers.
2.7: EC Directives and National Legislations

Over the past 20 years the European Commission has implemented a broad-based legislation aimed at reducing and/or controlling the levels of dioxins and furans released into the environment. This has been implemented as a result of the Tolerable intake recommended by the organisations listed in Table 2.14.
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The EC has introduced a total of 12 Directives, which are of varying degrees of importanceThese can be divided into the following categories: Waste incineration: this deals with the reduction of atmospheric emissions from industrial processes such as incineration. Aquatic environment: this aims to reduce the risk of fish and other aquatic life being contaminated. Animal nutrition: because dioxins are passed to humans through the food chain, the regulation of levels in animals is very important. Undesirable substances: (e.g. PCPs and PCBs) aimed at reducing widespread, lowlevel exposure by a variety of routes, i.e. chemicals. Major accidents and hazards: for the avoidance of accidental spillages.
Table 2.15 lists all the European Directives associated with dioxins in the environment, and also shows the ways that each country has progressed beyond the requirements of the Directive, especially in areas which are not addressed by EC regulations. It can be seen that most of the regulations have been focused on the reduction and/or control of dioxin emissions from the incineration of municipal solid waste (MSW), as this is regarded one of the major sources of these substances. Most countries have set a limit of 0.1 ng TEQ/kg for both existing and new incinerators used for MSW and hazardous waste. Although there are no directives for dioxin levels in air emissions from other industrial processes (which use high temperatures), most European countries have recognised that those types of industries may contribute to the overall emissions into the atmosphere. The levels of dioxins in ground water and discharge in the aquatic environment have been regulated, although the individual countries have not introduced regulations or guidelines beyond the Directive. Although there are no Directives covering the levels in soils, some countries have established guidelines for different soil classifications, for example, Austria, Finland, Germany, the Netherlands and Sweden have established guidelines ranging from <10 ng-TEQ/kg to <10,000 ng-TEQ/kg, with Sweden imposing the most stringent levels. Another significant area of attention is direct human exposure. Some EU countries have recommended a maximum tolerable daily intake (TDI) be introduced (some of which are lower than those limits of 10 ng-TEQ/kg body weight/day previously set by WHO) and that the levels in food such as milk and dairy products should also be regulated. Monitoring In order to ensure that European countries conform to the regulations and guidelines, nationally funded monitoring programmer have been set up or are being developed. Table 2.16 shows the countries that have successfully carried out monitoring on different
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environmental media. It can be seen that most programmes are undertaken by the northern countries, with Germany currently carrying out the broadest range. There is very little national monitoring in the southern countries with Greece, Italy and Spain having none at all. The UK monitors air, sewage sludge and food (dairy and fish), with a programme of monitoring the levels in humans being developed.
2.8: Dioxin / Furan Levels in Materials Suitable for the Construction Industry
Concrete blocks, clay bricks, mortar, plastering and plasterboard are commonly used in housing construction in the UK (Marshall and Worthing, 1995). These typically comprise raw materials such as water, clay, Portland cement, lime, aggregates, and/or chemical admixtures. In recent decades, other materials such as pulverized-fuel ash (PFA); furnace bottom ash (FBA); ground granulated blast furnace slag (GGBS); silica fume (SF); metakaolin (MK); incinerator fly ash (IFA); bottom ash (IBA); and, sewage sludge ash (SSA), have successfully been introduced into construction products (Sear, 2003; Chandra, 1997). The majority of raw materials used in construction products are subjected to thermal treatment during processing. Such treatments are carried out at temperatures above 700C and include cement kilns, incineration, coal combustion, flue gas treatment, fluidised bed combustion or electric arc furnaces. The range of materials used in construction products and their manufacturing processes are summarised in Figure 2.12. Construction Materials This section identifies the raw materials traditionally used in construction products, describes the processes carried out during their manufacture and summarises the literature available on levels of dioxins and furans detected in them. Portland cement (PC) Portland cement is the major constituent in construction products, with nearly 12.5 million tonnes produced in the UK annually (Department of Statistics, 2002). As can be seen in Figure 2.13, PC is manufactured from a combination of limestone, shale, iron ore and sand (Nawy, 1997). These raw materials are crushed and ground and the mixture is preheated to drive off water vapour in the cyclones. This is then fed into a rotary kiln and heated at temperatures between 1400C and 2000C. The cement clinker is formed in the kiln and deposited in the clinker cooler, whilst fine particulate matter (cement kiln dust) escapes upwards. The cooled clinker is then pulverised with gypsum, which improves the setting time when the cement is being used (Neville, 1995; World Bank Group, 1998; European Commission, 2001; Simmons, 2001). The clinker production process involves very high temperatures (1400C atmosphere, 2000C flame) and a long residence time (over 5 seconds - a minimum of 2 seconds is needed to suppress PCDD/F formation), it has therefore been speculated, that the levels of dioxins and furans in the product are negligible (Constans, 2003; Gossman, 2003).
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The available data for PCDD/F levels in cement clinker is very limited and is summarised in Table 2.18 and Figure 2.14. As can be seen, PCDD/F concentrations in PC and cement clinker do not exceed 1.0 ng I-TEQ/kg, even if waste fuel is burned and are considerably smaller than levels of other constituent materials of construction products and levels detected in soil and clay samples, which are considered a benchmark for comparison. Lime Lime is currently used in mortar, external rendering, and plaster-boards (Thomas, 1996) with approximately 1.7 million tonnes produced in the UK annually (European Commission, 2001a). Although it was the prime ingredients for lime plastering, this form of plaster declined around the 1950s (Marshall and Worthing, 1998). Limestone aggregate is heated in a kiln, during which the high temperatures (above 1000C) convert the calcium carbonate to calcium oxide (quicklime). The quicklime may be used directly, either in solid or powder form, or alternatively, treated with water to produce hydrated lime. No data concerning the levels of dioxins or furans in lime putty or hydrated lime was found in the literature. Pulverised-Fuel Ash (PFA) Pulverised-fuel ash (PFA) is the by-product from coal-fired power stations and the benefits from its addition to concrete have long been recognised (Joshi and Lohtia, 1997; Day, 1995; Malhotra and Mehta, 2002), with approximately 27% of the PFA produced in the UK being used in concrete production and in aerated autoclaved blocks (Sear, 2003). Pulverised coal combustion (predominantly of bituminous coal) involves grinding the coal aggregates into a fine powder (<100 m particle size), which is then sprayed into a furnace, where temperatures in excess of 1250C (Sear, 2003) convert the water (carried in pipes in the boiler) to steam, which is used to drive a turbine, thereby producing electricity (DTI, 2003; Malhotra and Mehta, 2002). The lighter fly ash particles (known as PFA) escape from the combustion chamber in the flue gases and are collected in electrostatic precipitators, cyclones or bag filters, where they cool rapidly, i.e. from over 1500C to 200C in a few seconds (Malhotra and Mehta, 2002). The PFA obtained is a finely-ground powder containing aluminium, iron, calcium and magnesium oxides (Harrex, 2003). Levels of PCDD/Fs in coal fly ash up to 80 ng I-TEQ/kg have been reported in the literature, as shown in Table 2.19 and Figure 2.14. It must be noted that, with the exception of fly ash cenospheres (generally used as filler in the plastic industry), dioxin and furan concentrations in PFAs from the UK are less than 10 ng I-TEQ/kg. The higher levels reported by the Danish ERA (60-80 ng I-TEQ/kg) may be attributed to different technologies adopted and varying raw materials. It is thought that dioxins and furans are unlikely to form on coal fly ash due to: (i) the high temperatures and adequate residence time needed for combustion; and, (ii) low chlorine and high sulphur contents in coal (Department of the Environment, 1989; Sear, 2003).
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Levels of PCDD/Fs in domestic coal fire soot range from 1.6 to 6,600 ng I-TEQ/kg (McKay, 2002) and may be attributed to lower temperatures achieved in domestic fires. Furnace Bottom Ash (FBA) Furnace bottom ash (FBA) is another by-product of coal fired power stations- During combustion, PFA particles fuse into fine molten beads of ash (FBA), which are collected into trays at the bottom of the furnace (Malhotra and Mehta, 2002). Around 15% of all ash produced in coal power stations is furnace bottom ash (FBA) and it is used either as an aggregate in lightweight aggregate concrete blocks or as a sub-base material (CIRIA, 1999; UKQAA, 2001), since FBA is not suitable as a pozzolana in concrete (Joshi and Lohtia, 1997). The reported levels of dioxins and furans in FBA are summarised in Table 2.20 and compared with levels in other materials in Figure 21.14. As can be seen, the dioxin/furan levels rarely exceed the UK limit of 50 ng I-TEQ/kg, and most often occur at levels ranging from 0.1 to 30 ng I-TEQ/kg (UKQAA, 2003; Environment Agency, 2002; McKay, 2002; Dyke et al, 1997; British Coal Corporation. 1995). Halliday (2003J has reported a level of 37 ng I-TEQ/kg detected in fly ash produced 1'rom the co-combustion of coal and refuse from the food industry. However, no other cocombustion ashes have been tested and their levels of dioxins and furans reported in the literature. Ground Granulated Blast Furnace Slag (GGBS) Up to 26% of blast furnace slag produced in the EC is used as PC replacement (approximately 1.5 million tonnes in the UK; Nawy, 1997; Hewlett, 1998) to enhance concrete performance (Haynes and Connell, 1996), whilst around 8% is used as aggregate for road construction (European Commission, 2001d). Integrated iron foundries consist of sinter plants and blast furnaces, as can be seen in Figure 2.15. Sinter plants produce a pre-designed ore (comprising iron oxides, carbon, lime, coal, and possibly oil or gas), which is fed into the blast furnace and heated up to 2000C. Molten iron collects near the floor of the furnace, below which slag products accumulate. The molten iron is sieved out, and the clay is then removed. GGBS is produced when the slag is cooled rapidly and ground into a fine powder for addition to cement (CIRIA, 1999). Blast furnace aggregate is produced when the slag is allowed to cool slowly and solidify into a grey, crystalline aggregate, which is often used as an aggregate in masonry units (Day, 1995; Chandra, 1997; Hewlitt, 1998; Simmons, 2001). Sintering plants are known sources of PCDD/F emissions (Table 2.14); however, very limited information on the PCDD/F emissions or their levels in slag exists. Buekens (2003) and the Environment Agency (2001) reported a level of 1 ng I-TEQ/kg (Table 2.21).
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Waste Materials Research into the utilisation of waste from industrial processes has been carried in order to try and minimise the amount being disposed of in landfill. These include a range of waste products, which physically and chemically could potentially be used as materials within me construction sector. Municipal Solid Waste The incineration of municipal waste has been practised since the first commercial incinerator was constructed in 1874 (Keily, 1997). Domestic waste incinerated each year in The UK exceeds 25 million tonnes in 15 incinerators. Although incineration reduces the volume of waste considerably (in some cases by as much as 90%) and the bottom ash (IBA) residue is being used as a replacement for natural aggregate in pavement engineering (Paine et al, 2000), there has been limned research on potential applications for the other waste produced, incinerator fly ash (IFA) in the UK. The major disposal routes for solid waste include recycling, energy recovery (incineration) and other disposal methods such as composting, with nearly 60% of UK waste being sent to landfill (DEFRA, 1998). There are various types of incinerators used to dispose of waste including mass-bum, refuse-derived and mono-incineration. The most popular type is mass-bum with approximately 68% of all incinerators opting for this process (Mujahid, 1993). A typical mass burn incinerator is shown in Figure 2.16. It can be seen that the waste is taken from the offloading depot and placed on a grate which moves through the combustion chamber, where temperatures can reach 850C (Environment Agency, 2001). The capacity of mass-bum incinerators usually ranges from 46 to 900 Mg waste/day. After the combustion process takes place it is necessary to install dust collectors in ihe system to ensure that concerns relating to the dust emissions into the atmosphere are eliminated. Under the EU Incineration of Waste Directive (2000/76/EC): (i) incinerator furnaces must be at least 850C; (ii) the waste material must not contain more than 1% halogcnaied organic substances (which can convert to dioxins and furans); and, (iii) the waste must reside in the furnace for at least 2 seconds (DEFRA, 2002). Incinerator Fly Ash (IFA) Figure 2.14 and Table 2.22 show the levels found in IFA from a number of worldwide sources, whilst Figure 2.17 shows those levels found in UK samples. It can be seen that the levels of PCDD/Fs in this material range from 50 to 28,000ng I-TEQ/kg, which exceed those recommended for use in construction. These high levels can be attributed to (i) more stringent EU air emission control targets (thus concentrating more dioxins and furans in the trapped ash) and (ii) additional formation of PCDD/Fs in the cooling flue gases where the material is trapped for a sufficient period of time (DEFRA, 2002; Environment Agency, 2002; McKay, 2002). Ozvacic (1986) and Vogg and Stieglitz (1986) both reported that dioxins are more likely to reform after the flue gases have left the combustion chamber, whilst the US
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EPA (1989) reported that when the flue gases are passed through air pollution control devices (operating at temperatures in the region of 200-400C) the amount of dioxins and furans formed are over 100 times more than in the combustion chamber. However, the injection of activated carbon is an important contribution to the fly ash, which can reduce dioxin and furan concentrations in the flue gases by 80-95% (Cudahy and Helsel, 2000). Moreover, Pera and Ambrose (2000) suggested that in order to reduce dioxin and furan formation, quenching the flue gases immediately after they emerge from the combustion chamber would be required. Finally, eliminating chlorinated plastics and other sources of chlorine would ultimately prevent the formation of these compounds. Incinerator Bottom Ash (IBA) Figure 2.14 and Table 2.23 show the levels from a number of IBA samples tested from various sources, whilst Figure 2.18 shows the PCDD/F levels found in IBA obtained from a number of MSW incinerators from within the UK. It can be seen that most of the ashes are within the 50 ng I-TEQ/kg margin for construction materials. This is due to the IBA being discarded from the 850C furnace, and immediately quenched in a water bath, thus preventing dioxins and furans from forming within the 200C to 600C "Dioxin Window" (Dan et al, 2003). McKay (2002) reported that the levels in a mixed ash (a combination of IFA and IBA) are in the region of 106 to 466 ng I-TEQ/kg. Waste Water Treatment Sewage Sludge Sludge is formed during waste water treatment. Waste water is a combination of the liquidcarried wastes removed from domestic and industrial establishments together with ground water, surface water and storm water (Kiely, 1997). It may contain organic, inorganic and toxic substances, as well as pathogenic micro-organisms. In its un-treated form, wastewater cannot be disposed of, since: (i) the biological decomposition of the organic material can reduce the amount of oxygen required for aquatic life; (ii) the pathogenic micro-organisms are a health hazard to humans; (iii) the toxic compounds (e.g. heavy metals) can be dangerous to plants and animals; and, (iv) the phosphate and nitrogen may lead to uncontrolled growth of plants. There are regulations governing the composition of effluent discharged from sewage treatment works. To achieve these set limits in a typical treatment plant, the waste water can be directed through a series of physical, chemical and biological processes each with a specific waste load reduction task (Kiely, 1997). Figure 2.19 shows possible routes for sewage sludge. Sewage sludge can contain dioxin and furan I-TEQ concentrations, which are comparable with those of MSW incinerator fly ash. As shown in Table 2.25, this may be due to the source of the sludge, particularly if the effluent is produced from industrial sources. However, the data is limited, and further studies may be needed to confirm this.
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Sewage Sludge Ash (SSA) Sewage sludge generation in the UK today amounts to approximately 1.2 million tonnes annually. There are various disposal options, including agriculture, landfill and incineration. Landfill disposal of sewage sludge has become increasingly expensive as a result of the Landfill Tax Directive, whilst alternative disposal methods (mainly land spreading and incineration) have become more popular (Werther and Ogada, 1999). As a result, nearly 25% of all sewage sludge produced is incinerated (Environment Council, 2002; Anderson and Skerratt, 2003), whilst cement producers and coal-fired power stations have been known 10 use sewage sludge pellets as refuse-derived fuel (ENDS Report, 2002c). Fluidized-bed combustion is the most popular type of technology, with all UK waste water treatment plants adopting this technique. This incinerator is capable of high removal efficiency of PCBs and input PCDD/Fs, and produces low to negligible emissions of dioxins from coal, waste and/or sewage sludge incineration (Stationery Office, 1999; Wasteguide, 2002; Anthony and Granatstein, 2001). No bottom ash is produced by fluidised bed combustion (Werther and Ogada, 1999), as the medium (sand) is recycled back into the system. Table 10 shows that the levels in SSA occur at over 1.0 order of magnitude below the 50 ng I-TEQ/kg limit, although further information is needed, in order to conclude whether these levels are consistent with SSA. Although dioxins and furans are usually found in emissions from incineration of municipal, hazardous and hospital waste, Liem and van Zorge (1995) reported that sewage incineration is also responsible (see Table 2.26) and that the PCDD/F emissions in the UK approximate 1150 g TEQ/year. Figure 2.14 and Table 2-27 show the levels in SSA, and it can be seen that they are below the 50 ng I-TEQ/kg limit. Cement Kiln Dust (CKD) Cement Kiin Dust (CKD) is a by-product of the manufacture of Portland cement (PC) and is collected from the cement kiln exhaust gases. The material consists of particles of cement clinker, condensed inorganic volatiles and partially calcined feedstock materials (Kessler, 1995) and, although derived from the same raw materials used to produce PC, differs chemically, mineralogically and morphologically. Portland cement is produced in a large rotating kiin where air moves into the kiln with the fuel providing the combustion oxygen situated at the base. The flow of gas is, therefore, against the flow of the raw material resulting in the gas flow 'picking up' partially burnt raw materials and carrying them the 'wrong way' up the kiln (Cornish and Coleman, 1995). Subsequently, the volatilised compounds condense downstream of the burning zone and become fume particles (generally smaller than 0.1 to 10 m in size), which accumulate on the surface of existing dust particles (as shown in Figure 2.20). This process is repeated as the dust particles evaporate and re-circulate within the kiln. This dust, which is known as cement kiln dust (or CKD) consists of fine particles of volatiles such as sodium, potassium, chlorides and sulfates, as well as volatile metal compounds (Davies, et al, 1975).
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The particulate is captured, either by an electrostatic precipitator, or by bag filters in the flue gas stack (World Bank Group, 1998). Cement kiln dust can be recycled back into the preheating cyclones and the cement kiln, in order to reduce the raw material demand and the energy costs incurred (Livesey, 1996; Halliday, 2001). CKD usually contains higher concentrations in comparison to cement clinker, although none have been reported to exceed 50 ng I-TEQ/kg (see Figure 21.14 and Table 21.28). Dyke et al (1997) reported on a range of 0.001 to 30 ng I-TEQ/kg in clinker samples from cement plants across the UK (some of which may have been using wastes). Greenpeace (2003) reported contrasting values of 0.03 and 35 ng I-TEQ/kg, when comparing clinker produced from coal combustion and hazardous chemical incineration, respectively, emphasising that incineration of waste increases the dioxin and furan levels in the collected dust. Moreover, Constans (1998) speculated that dioxins and furans emitted from cement kilns may originate from within the raw materials, and the Danish EPA (1997) reported on PCDD/F concentrations in two clay samples, one value being above the 50 ng I-TEQ/kg limit (Figure 2,14). However, it cannot be concluded that such levels occur in clay or shale, or may affect the levels in the clinker or CKD, owing to the lack of data. Construction Products Masonry walls typically comprise clay bricks, tiles, concrete blocks, plasterboard and external rendering. These materials have been used in housing construction throughout the 20th century, particularly after the First World War (Beall, 2001). Since the 1970s, cavity walls for housing have generally consisted of a concrete block or clay brick outer layer, and a concrete block inner layer (Marshall and Worthing, 1995). This section reports on the materials/products used within the construction sector and describes the manufacturing techniques involved in their production. Clay Bricks Approximately 2.5 billion clay bricks are produced in the UK each year and are used in various construction projects. The manufacturing techniques adopted are illustrated in Figure 2.21. The shale and clay materials for extruded brick are mixed with a pigment and water. This mixture is forced by means of an auger through a die having the shape of the brick. Prior to entering the die, the material passes through a vacuum changer that reduces the amount of air in the mix resulting in a denser, more homogeneous product. Prior to entering the kiln, the unfired or green brick must be properly dried. Generally, the drying process is done by placing the green bricks in enclosed dryers, which utilize excess heat from the cooling kiln. The next step is burning or firing the green bricks. These pass through the long length of the kiln on a continuous procession of cars moving on rails, much like a small railroad train. The continuous tunnel kiln employs a combination of vertical and horizontal drafts. The preheating, burning and cooling is done in zones varying in temperatures between 900C and 1250C. Fire clay is mainly composed of quartz, and clay minerals, enriched in iron oxides (Brick Development Association, 1994; Dept. of Statistics, 2002).
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Concrete Blocks The use of concrete blocks has become popular during the last 70 years due to the relatively low cost compared to that of brickwork (Marshall and Worthing, 1995), with over 90,000 sq. metres of blocks produced in the UK in 2000 (Dept. of Statistics, 2002). There are various types of concrete blocks available in the UK, ranging from concrete breeze block to lightweight and aerated autoclaved concrete blocks. Ordinary concrete blocks are produced, by mixing the raw materials together with water. The mixture is then cut into blocks and allowed to set (Simmons, 2001). Aerated concrete blocks are engineered to combine low density, high strength, high thermal performance and good fire resistant properties. The low density is achieved by introducing stable air voids within the hardened cement paste or mortar. These air voids are usually achieved by using finely divided aluminium powder. The aluminium powder reacts with the calcium hydroxide or alkalis in the cement to produce hydrogen bubbles, which are discrete and are typically smaller than 1mm. Autoclaving (Figure 2.22) is a high-pressurised steam curing technique (usually at l80C) used to obtained higher strength concrete blocks, which are cut from a mass of concrete during factory production. The benefits of autoclaving are attributed to a rapid pozzolanic reaction between PC and fine siliceous sand or PFA (or a mixture of the two materials). The majority of lightweight and aerated concrete blocks include PFA (blocks can contain up to on average 80% PFA), with 16% of all PFA produced in the UK used for their production (Marshall and Worthing, 1995; UKQAA, 2001; Sear, 2003). Plasterboard Plasterboard primarily consists of gypsum, although nowadays fine aggregate is also included as a retarding agent, to prevent the gypsum setting too quickly. Gypsum ore is crushed, dried, and heated to approximately 225C in a rotary calciner in order to eliminate moisture. The product is passed through a tube mill (wherein steel spheres crush the gypsum into a finer powder), and placed into storage bags for distribution (Olin et al, 1995). Gynsum is the prime material used in plasterboard, although BS 1230 allows additives to be included. Mixing gypsum with water (to produce plaster of Pans) produces a substance which sets too quickly. Carlite gypsum was introduced in the 1950s, which comprised a mixture of gypsum, line aggregates, and water. Carlite gypsum is used nowadays, although admixtures may also be included. This material is easier to produce on site, has better thermal insulation, and is fire resistant (Marshall and Worthing, 1995). In order to prevent rot, plasterboards are impregnated with preservatives. In addition to gypsum, the composition of plasterboards may include lime and Portland cement, in addition to fine aggregate (Marshall and Worthing, 1995; Thomas, 1996). BS 1230 requires that gypsum-based plasterboards contain paper wrapping, and should have "additives to impart additional properties".
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Data regarding the levels of dioxins or furans in clay bricks and concrete blocks are shown in Figure 2.14 and Tables 2.29 and 2.30. It can be seen that both aerated breeze blocks (containing PFA) and clay bricks (as shown in Table 21.30) contain very low levels of dioxins and furans. Autoclaved concrete blocks containing PFA were analysed by the [JKQAA - on average they contained around 25 ng I-TEQ/kg; half the UK limit. Blocks containing Edmonton mixed ash (fly ash mixed wnh IBAJ comprised much higher levels, in breach of the 50 ng I-TEQ/kg limit. This is to be expected, given the contrast between the levels of dioxins and furans (in I-TEQ) between IFA, and IBA.
3: PROGRAMME OF WORK
The programme of work is shown in Figure 3.1. The approach adopted was be a combination of: (i) carrying out a comprehensive review of the literature available; (ii) obtaining construction materials/products from a number of sites; (iii) carrying out an analytical procedure to establish the levels of dioxins and furans; and, (iv) disseminating these results.
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4: OBTAINING CONSTRUCTION MATERIALS

4.1: Sampling Strategy
A wide range of housing schemes across the UK were identified through contacting housing associations. The study was then divided into two separate data sets: Data Set 1: samples of products used in new construction, to evaluate the present market. Data Set 2: samples of products used before 1980, obtained from the both existing housing elements and demolition sites, to assess the products used at a time when the issue of potential presence of dioxin and furan compounds in them had not risen.
4.2: Samples Collected

Data Set 1: New Housing Developments (Names of organisations, housing associations and contractors have been omitted) The type and quantity of materials obtained from new construction are summarised in Table 4.1. In addition, a soil sample was collected (wherever possible) from the site area, to be used as a reference. Samples from new developments have been obtained from around the UK, as can be seen in Figure 4.1. Details of the sites (Housing Association, location, OS Grid reference, type of construction, number of units) and samples (type, manufacturer) obtained from England, Scotland, N Ireland and Wales are summarised in Tables 4.2 to 4.13. Data Set 2a: Existing Housing (Names of organisations, housing associations and contractors have been omitted) Cored samples from walls within existing houses were collected from various sites around the UK. These sites are shown in Figure 4.1 and Table 4.14. Data Set 2b: Demolition Waste The geographical distribution of sites where demolition samples were obtained from can be seen in Figure 4.2, whilst the suppliers of the samples and exact site locations are summarised in Table 4.15.
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5: TEST METHOD ADOPTED FOR THE ANALYSIS OF DIOXINS AND FURANS IN CONSTRUCTION MATERIALS
There are various test methods available for the detection and determination of the dioxin/furan concentration in a solid sample. The method adopted (EPA Method 1613: 1997), is for determination of tetra-chlorinated dibenzo-p-dioxins (CDD) and dibenzofurans (CDF) in water, soil, sludge, tissue and other sample matrices by GC/MS.
5.1: EPA 1613 Test Procedure

Sample Preparation The first stage involves 'spiking' a dry sample with a diluted compound spiking solution (which contains all CDDS/CDFs to be analysed). The sample is ground to a fine powder (particles <1mm). 10g of sample is measured out and placed in a clean beaker and spiked with 1.0ml of the diluted spiking solution (diluted 1:50 with acetone). The sample is then stirred for 1 to 2 hours. Extraction Method According to the EPA Standard (1613) the sample should be subjected to extraction and concentration in order for all the dioxins/furans in the sample to be 'extracted' with a solvent known not to contain such congeners. Currently, the standard recommends that the Traditional (manual) Soxhlet should be used (apparatus shown in Figure 5.1). When preliminary extraction tests were carried out in the laboratories, there were problems associated with this method: The overall time scale: The total time for pre-extraction and extraction could take up to 27 hours. The use of toluene as a solvent: The standard specifies that hexane should be used as a medium in the extraction process and that it should be heated to boiling point and left for at least 16 hours (overnight). This is not permitted under health and safety regulations. Leaving the sample unattended: The water has to be drained from the reflux at 1-2 hours and then again at 8-9 hours. The apparatus should then be checked to see if overflowing of water occurs. It is not practical (or permitted) to leave the apparatus overnight, and slopping the procedure every day may lead to inaccurate results. The amount of solvent required: For a successful extraction, the amount of solvent required was such that additional concentration was required in order to obtain the con-eel sample size.
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In light of these problems, it was decided that an automatic soxhlet should be used. Soxtherm, which is an automated version of the traditional Soxhlet apparatus and can be used for the determination of pollutants in environmental samples, was used (Figure 5.2). The process is fully automatic and is especially suitable for residue analysis and the extraction process is performed in five phases to ensure complete extraction, as shown in Figure 5.3:
Phase 1: The sample, which is held within a thimble, is immersed in boiling solvent and the extractable material (PCDD/PCDF) is released from the sample. Equilibrium is set up between the extract in solution and that which is still on the sample surface (Extraction Stage). Phase 2: The level of the solvent is lowered below the extraction thimble by continuous heating the solvent. The excess solvent is collected in the rear of the solvent recovery tank. Phase 3: The PCDD/PCDFs are extracted by the reflux, condensed solvent and are collected in the solvent, below in the extraction breaker (Rinsing Stage). Phase 4: The bulk of the solvent is distilled over into the solvent recovery tank for later use. Phase 5: The solvent is heated until totally evaporated and extraction beaker is automatically lifted from the hotplate (Evaporation Stage).
The Soxtherm extraction programme is based on the Dean-Stark extraction methods set in the EPA Method 3541 (USEPA, 1994b). It was reported by McKay (2002), Harrison (2001) and USEPA (1994b) that by using an automated system, a more efficient extraction of compounds could be conducted. Tests were carried out by Gerhardt (2001) to establish the competence of Soxtherm compared to that of the manual Soxhlet extraction. It was found that the Soxtherm apparatus was more efficient. Using this information, the extraction and rinsing limes were established and hexane used as the extraction solvent. Extract Clean-up The clean-up of extracts has been developed since the laic 1970s, when i; was discovered that biological samples and sediments contained organic compounds (namely phenols), which interfered with mass spectrometry analysis (Petrovik et al, 2002; USEPA, 1994a; Afghan et al, 1987; Lamparski and Nesirick, 1980). The clean-up phase involves passing the extracts through a column of layers of acid rich silica gel and alumina powder.
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Micro Concentration and Solvent Exchange In order to prepare the clean extract for gas chromatography/mass spectrometry, the extract has to be concentrated to a volume of 200 L, transferred into an appropriate vial, and evaporated down to 20 L. The extracts are then stored at temperatures of below minus 10C until required-preferably within 1 week.
5.2: Gas Chromatography/Mass Spectrometry

Gas chromatography/mass spectrometry (GC/MS) is a technique proved suitable for analysing dioxins and furans and is recommended in the EPA 1613 method (Petrovic et al, 2002; Samos and Galceran, 2000; USEPA, 1994). The GC/MS instrument represents a device that separates chemical mixtures (the GC component) and a very sensitive detector (the MS component) with a data collector. Gas Chromatography (GC) Gas chromatography is a chromatographic technique that can be used to separate organic volatile compounds. Dioxins and furans occur as a combination of congeners, which must be separated prior to analysing with gas chromatography, is considered to be the most suitable method for this purpose. It is renowned for its high precision, and us use in identifying organic molecules at both medium and extremely low concentrations (Santos and Galceran, 2002; Skoog et al, 1996; De Jong and Liem, 1993; Skoog and Leary, 1992). A gas chromatograph consists of a flowing mobile phase, an injection port, a separation column containing a stationary phase, a detector and a data recording system (as shown in Figure 5.5). The mobile phase is generally an inert gas, such as helium, argon or nitrogen. The sample is injected using the injection port (which consists of a rubber septum through which a syringe needle is inserted to inject the sample), where it is immediately vaporised and swept into the heated column (>250C) by the carrier gas. The sample flows through the capillary column experiencing normal separation. Capillary columns are a thin (250 m) in diameter) fused-silica capillary typically 10-100m in length, that has a stationary phase coaled on the inner surface. The column holds the stationary phase and the mobile phase carries the sample through it. These columns provide much higher separation efficiency than other packed columns, but can be overloaded by too much sample (Mendham et al, 2000). Sample components mat partition strongly into the stationary phase spend a greater amount of time in the column and are separated from components that are predominately in the mobile phase and pass through the column faster. The stationary phase separates the congeners al different stages of the process, and each congener emerges from the column opening into the capillary column interface. Mass Spectrometry (MS) Mass spectrometry (MS) uses the difference in mass-to-charge ratio (m/e) of ionized atoms (or molecules) to separate them from each other and is used to quantify components. Groups of each type of dioxin and furan molecule, once separated by gas chromatography,
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enter the MS. Figure 5.6 gives a schematic of the various stages involved in traditional MS. It can be seen that the molecules are split into fragments in the ion source, and the molecular fragments accelerate through a vacuum in the analyser tube. The momentum of the fragments of each dioxin/furan group is recorded; the momentum varies between each type of dioxin or furan group, and is also affected by the atomic mass. The samples are therefore "spiked" with a solution containing the 17 potentially toxic dioxin and furan groups, which contain heavier 13C atoms. When each type of dioxin or furan is being measured using the mass analyser, the concentration of (non-13C-comaining) dioxins and furans from the solid samples are compared with the set amount of 13C-containing dioxins and furans. The mass spectrometer is illustrated in Figure 5.7. The gaseous congener samples are individually removed from the gas chromatography column, and drawn into a "reservoir" (around 3 to 5 litres of gas) at the Ion Source. The congeners are then bombarded by electrons (electrocution) under the filament, and drawn through the acceleration slits. These contain the opposite charge to that of the bombarded congener molecules and their fragments, thus causing the fragments to accelerate towards the analyser tube, until they reach the required velocity. The fragments in the analyser tube travel through a vacuum, in order to prevent interference by other gas molecules (which would collide with the PCCD/F fragments) (Dean, 1995). Mass spectrometry is normally used to identify and/or measure the atomic mass of molecules or isotopes. Each congener analysed is accompanied by the same congener; however, the latter carries a carbon-13 atom isotope, and is therefore heavier. The heavier congener (from the spike solution) "falls below" the lighter congener in the analyser tube, and the mass spectrometer can study these molecules separately. As there is a known amount of isotope-carrying congener, the amount of the normal congener (from the concrete sample) can be measured, as illustrated in Figure 5.8. The spectrometer records the concentration of each congener in graph form (see Figure 5.9), showing the abundance of each fragment of the original congener (above). For each congener there is an individual pattern. From these patterns, the computer attached to the MS is able to deduce the concentration of each dioxin or furan congener, against the set concentration of its 13Ccarrying accompaniment. Tandem GC/MS Development Work (or GC-MS/MS) Due to the specificity and sensitivity of dioxin and furan compound analysis, powerful analytical tools, such as high resolution gas chromatography coupled with high resolution mass spectrometry (HRGC/HRMS) has become the reference method in this field. Mass spectrometry is a very powerful method to analyse the structure of organic compounds, but suffers from three major limitations: compounds cannot be characterised without completely clean samples; this technique has not the ability to provide sensitive and selective analysis of complex mixture; and, big molecules like dioxins and furans are very complex and very difficult to interpret.
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Moreover, HRGC/HRMS is a highly expensive method and alternative methods have been researched (Focant et al, 2001, Helen et al, 2001), namely, capillary column gas chromatography/ mass spectrometry (GC/MS/MS) or tandem spectrometry. This is a low resolution technique, which uses ion trap spectrometers to identify and analysis dioxins and furans compounds in various media. MS/MS or tandem mass spectrometry was first introduced in the 1970s and was quickly accepted in the analytical community. The technique has been used for the clarification of unknowns, and for analysis of complex mixtures with minimum sample clean up. Development in the mid-1980s advancing the popularity of MS/MS included the availability of powerful data system able to control the MS/MS experiment. MS/MS is used to produce structural information about a compound by fragmenting specific sample ions inside the mass spectrometer and identifying the resulting fragment ions. This information can then be pieced together to generate structural information regarding the intact molecule. Tandem mass spectrometry also enables specific compounds to be detected in complex mixtures on account of their specific and characteristic fragmentation patterns. A tandem mass spectrometer (or ion trap) is a mass spectrometer that has more than one analyser; in practice usually two (see Figure 5.10). The two analysers are separated by a collision cell into which a gas is admitted to collide with the selected sample ions and bring about their fragmentation. The basic modes of data acquisition for tandem mass spectrometry experiments are as follows: Product or daughter ion scanning: the first analyser is used to select user-specified sample ions arising from a particular component; usually the molecular-related (i.e. (M+H)+ or (M-H)-) ions. These chosen ions pass into the collision cell, are bombarded by the gas molecules which cause fragment ions to be formed, and these fragment ions are analysed, i.e. separated according to their mass to charge ratios, by the second analyser. All the fragment ions arise directly from the precursor ions specified in the experiment, and thus produce a fingerprint pattern specific to the compound under investigation. Precursor or parent ion scanning: the first analyser allows the transmission of all sample ions, whilst the second analyser is set to monitor specific fragment ions, which arc generated by bombardment of the sample ions with the collision gas in the collision cell. Multiple Reaction Monitoring (MRM): where both of the analysers are static and user-selected specific ions are transmitted through the first analyser and userselected specific fragments arising from these ions are measured by the second analyser. This methodology is used to confirm unambiguously the presence of a compound in a matrix e.g. drug testing with blood or urine samples. It is not only a highly specific method but also has very high sensitivity.
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Essentially, the development work for GC/MS/MS was divided into three stages, namely: A: identifying the 17 compounds and retention times The GC/MS/MS was carried out using a Saturn 2000 GC/MS/MS coupled with a 3400 gas chromatography unit and an 8200 autosampler (Varian, USA) and Saturn 6.1 software was used. PCDD/F compounds were separated using DB-5 (30m x 0.25mm x 0.25 m) column (Varian, USA). The GC conditions were optimised in order to separate all 17 compounds, and these conditions are given in Table 5.2. Data imputed into a computer program is shown in Figure 5.11. It can be seen that the temperature within the column increases at different rates until a maximum temperature of 315C is achieved, and the total time was 35 minutes. It must be noted that the initial run time was 55 minutes, but this was optimized (reduced) through development work (i.e. increasing staring temperatures and rate of temperatures etc). A standard mixture, containing all 17 PCDD/F native compounds (together with the 13Clabelled isotopes), was injected into the system using full scanning mode. The trace in Figure 5.12 was obtained using the 35 minute GC programme. In order to successfully identify each compound, a 'mass spectra' was obtained and checked against those found in the NIST library (a data base containing the mass spectra for thousands of compounds). Figure 5.13 illustrates a mass spectra for the compound 1,2,3,7,8-PeCDF. It can be seen that the most abundant spectra for this compound is 340 m/z. This is known as the 'parent ion'. The mass spectra for the remaining compounds are given in Figures 5.14 to 5.23. The retention time, coupled with the mass spectra are the two ways in which the operator can correctly identify the dioxin/furans during testing as interference from other compounds may make this task difficult otherwise. Table 5.3 gives the retention lanes and the parent ion for each compound. B: MS/MS Optimisation There are four steps involved in a typical MS/MS analysis, namely, ionization, parent isolation, collision-induced dissociation (CID) and mass analysis of the daughter ion. In order to successfully capture the parent ions and earn,' out a dissociation (i.e. and obtain the daughter ion), the first step of the scan function is the ion storage, during which sample ions formed in the ion source arc trapped in the mass analyser. During this storage period (= [parent isolation window] [time]), a broadband waveform is applied (ions outside the parent isolation window - m/z range are not stored in the trap. The isolation of the parent ion can now take place. Figure 5.24 (a) shows the data required for the Varian software. The third step involves applying a voltage to the ring electrode and the waveforms applied on the end-cap electrodes (CID), to ensure that the parent ion fragments, therefore producing a daughter ion (corresponds to the loss of COC1 (m/z = 63) for the parent ion). The optimum CID amplitude and voltage (energy) required have been determined by running an automated method development (AMD) for each compound. The CID amplitude is calculated using a standard equation and voltage is determined by increasing the energy from 0.5 and 5.0 volts in Increments of 0.5. Individual scans are carried out for each voltage
41
and the mass spectra of the daughter ion analysed. The optimum values were used (i.e. where the daughter is most abundant and the parent is least abundant). Theoretically, there has to be an optimum for each compound, as an energy (voltage) of 0.0 will produce no dissociation, and an energy of 5.0 will cause the daughter ions to fragment further. This method was carried out on each PCDD/F. and an illustration of die mass spectra for the daughter ion for a PCDD compound with the optimum values applied is shown in Figure 5.25. The daughter ions and the resulting CID amplitudes and energies are shown in Figure 5-24 (b) and also given in Table 5.4. The mass spectra for the daughter ions for the remaining PCDD/Fs are given in Figure 5.26 to Figure 5.33. The EPA 1613 Standard specifics that a standard 'spiking' solution be injected onto the sample before the extraction stage is carried out, which contain 16 of the 17 "C -labelled isotopes for each PCDD/F. This is used as a secondary check during testing and to ensure that the compounds are not lost during the extraction and clean-up stage. Multiple reaction monitoring (MRM) was used to obtain the mass spectrum for all the 13C-labelled isotopes. Table 5.4 gives the parameters used to achieve this. C: calibration of apparatus and Limit of Detection Four standard solutions, containing all 17 PCDD/F compounds, together with the 13Clabelled compounds, were used to calibrate the Varian GC/MS/MS. and the average taken. Table 5.5 gives the concentrations of PCDD/Fs in calibration solutions. The traces for native compounds and the re-labelled isotopes present in the calibration standards are shown in Figures 5.34 to 5.37. The standards were run several times and the areas beneath each 'compound peak' were used to determine the concentrations and calibrate the machine. In order to determine the limit of detection (LOD) for the equipment, aliquots of CS2 calibration solution were diluted to various concentrations: 0.5CS2 0.25CS2 0.2CS2 0.1CS2 0.05CS2 (2:1 dilution) (4:1 dilution) (5:1 dilution) (10:1 dilution) (20:1 dilution)
For each congener, the limit of detection is the lowest possible amount of an analyte that is not detectable for that sample and Table 5.4 gives these limits for each congener. Table 5.4 also shows the I-TEQ value (ng/kg) calculated for the limit of detection of the equipment, and this was found to be 4.0 ng/kg.
42
6: RESULTS
6.1: Precision and Recovery
In order to determine the proportion of dioxins and furans which could be potentially lost from a sample during the extraction and clean up stage, it was necessary to carry out a Precision and Recovery (PAR) test (as recommended in EPA 1613). This is when a commercially prepared solution (containing spike compounds) is injected into sample extracts and then subjected to the exact same procedure as a normal test sample. EPA 1613 limits the percent recovery for the dioxin and furan congeners and these values are given in Table 6.1. However, when PAR tests were carried out it was found the recovery was not acceptable (less than limits set by EPA 1613). It was determined, thorough trial and error testing, that the clean-up stage was responsible for the largest proportion of the lost congeners. The EPA Method 1613 standard recommend the clean-up of extracts by using silica gel and alumina, respectively. A range of clean-up methods were developed (as shown in Table 6-2) and it was found that a procedure outlined by Martens et al (2002) produced the most satisfactory results. Modified Method Alumina powder and silica gel were heated at 105C for at least 48 hours prior to use, and were stored in the oven in-between experiments. Immediately before being used, both materials were left in a desiccator to cool. 1.5g (0.1g) of alumina powder was added first, followed by 3.0g (0.2g) of silica gel. The final layer on top comprised sodium sulphate; this removed moisture from the extracts. Prior to pouring the extract through the column, 50mL of hexane solvent was passed through the column In order to remove both moisture and any contamination. This was collected and discarded. As soon as the last of the solvent entered the column filter (when about 5mm of solvent covered the filter), the sample extract was poured in. Some hexane was added to the Soxtherm beaker to wash out any remaining extract, and the washings applied to the column also. A clean 100ml beaker was used to collect the purified extract. Afterwards 50mL of hexane was passed through the column in order to wash out dioxins and furans trapped within the column. The materials were then disposed of, and the column was thoroughly cleaned with detergent and then dried. The percentage recovered for each dioxin/furan congener, using this modified method, is given in Table 6.1, and it can be seen that these satisfy the EPA 1613 limits.
6.2: Results
New Housing Developments Results for the samples obtained from England, Scotland, Wales and N Ireland are given in Tables 6.3 to 6.6. No dioxin or furan congeners were reported to be found in these samples. In almost all samples, the results showed that there was no 'peak' present at the retention time assigned to a particular congener. However, there were incidences were a minor peak
43
was detected, therefore indicating that the native dioxin or furan was present. Upon further investigation, through identification of the mass spectra, it was concluded that these particular isotopes were not dioxins or furans. One example was the Scottish sample Ns4. This particular test sample had produced a chromatograph which suggested that dioxins and furans were present. However, by inspecting the mass spectra of the peaks it was found not to be the same as that identified and verified using MIST library facilities. Existing Dwellings and Demolition Waste Table 6.7 contains the results for the dioxin/furan concentration in samples collected from existing houses. No peaks were present, therefore suggesting that there were no dioxins or furans present or that the levels are below the detection limits of the instrumentation. The results for the samples retrieved from demolition sites are given in Table 6.8. The results were similar to those found for the samples taken from existing dwellings. Soil The soil sample results are given in Table 6.9. The background noise was much higher (compared to the GC-MS/MS scans for the extracts of other materials), suggesting that there were interferences from other compounds which have a similar structure to dioxins and furans (PAHs). As mentioned in Chapter 2, the reported levels of dioxins and furans in soils can range from negligible amounts to over 200ng I-TEQ kg; higher concentrations are expected in urban and polluted soils.
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7: CONCLUSIONS
The overall aim of the study was to determine the levels of dioxins and furans in a variety of construction materials and products from UK sources. The main objectives of the project were to collect samples of construction material/products in new dwellings and those (older than 1980) from various sites throughout the UK, and to perform tests using GC/MS to identify and determine levels of dioxins and furans in each sample. The following conclusions were drawn from the work carried out:
Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are two groups of highly toxic organic compounds, which are refractory lipophilic pollutants formed by the interaction of chlorophenols (211) in total). The toxicity varies considerably for congener, with the 2,3,7,8 TCDD having the highest toxicity of all. The toxicity of the compounds is the main concern, with only 17 congeners being assessed when measuring dioxin/furan levels. The standard is to express the total concentration in terms of toxic equivalent (TEQ value in ng/kg) Dioxins and furans formation is generally unintentional and usually associated with combustion processes in which chlorine is present. Potential sources include industrial (incineration of municipal waste, metal smelters, cement and lime manufacture); chemical (pulp and paper, PVC, chlorophenols and cooling fluids); and, non-industrial (wood burning and car emissions). The main route by which humans are exposed to dioxins and furans is through the ingestion of food, although exposure can also be through inhalation and skin contact with contaminated materials. The levels of dioxins and furans in the environment (air, soil, vegetation, food and humans) have decreased since the 1960s, mostly due to the implementation of broad-based legislation (EC Directives and Regulations). The levels of dioxins and furans in construction products/materials was found to be limited, although the results reported were found to Wow the level of 50ng/kg, with the exception of some PFA samples and fly ash derived from the incineration of municipal waste. Samples were collected from New Housing Developments (160 total), existing housing and demolition (18 total). These included concrete blocks/bricks, clay bricks, plasterboard, mortar, fly ash, Portland cement and lime. The samples were collected from 37 sites around the UK. There are various test methods available for the detection of dioxins and furans, with EPA 1613 Standard being the most widely used commercially. This test method
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involves 'extracting' the dioxins and furans from a samples with a solvent using Soxhlet extraction, in the form of a liquid sample. This sample is then passed through a clean-up process to ensure that any interfering congeners are removed. The sample is then tested using high resolution gas chromatography and high resolution mass spectrometry (HRGC/HRMS). The HRGC/HRMS instrument is a highly sensitive device that separates chemical mixtures (GC component) and a very sensitive detector (MS component) with a data collector. Due to the highly sensitive nature of the test (and availability of equipment) it was necessary to develop a new test method using GC and tandem MS/MS. This is a low resolution technique, which uses ion trap spectrometers the clarification of unknowns, and for analysis of complex mixtures with minimum sample clean up (such as dioxin and furan congeners). Quality control checks were carried out prior to lest, i.e. identification of PCDD/F congeners, their retention time and the mass spectra of each. The inclusion of a 'spike solution' allows the detection of a non-natural occurring labelled congener. This 'peak occurs at the exact same time as the native congener. Overall, dioxin and furan congeners in the construction materials were either (a) not present or (b) found to be below the limit of detection of the GC/MS/MS apparatus. I-TEQ values were found to be 8.88ng/kg when concentrations were below the limit of detection and percentage recovery was taken into consideration.
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Dhir, Halliday and Sutherland. UK SURVEY OF DIOXINS AND FURANS IN CONSTRUCTION PRODUCTS.

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1

UK SURVEY OF DIOXINS AND FURANS IN CONSTRUCTION PRODUCTS

R. K. Dhir, J. E. Halliday, M. A. Sutherland

Produced at the University of Dundee, June 2004 REVISED JUNE 2013

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

CONTRIBUTORS TO THE PROJECT (information withheld)

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

LIST OF TABLES (table no., page no.)

LIST OF FIGURES (figure no., page no.)

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

1.3: Beneficiaries and Expected Impact

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

2.1: Chemistry of Dioxins and Furans

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

2.2: Formation of Dioxin/Furan Compounds

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Cl2 + SO2 + H2O

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

2.3: Potential Sources

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

2.4: Potential Exposure

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

2.5: Dioxin / Furan Levels in the Environment

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

2.6: Associated Risks

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

2.7: EC Directives and National Legislations

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

4: OBTAINING CONSTRUCTION MATERIALS

4.2: Samples Collected

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

5.1: EPA 1613 Test Procedure

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

5.2: Gas Chromatography/Mass Spectrometry

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.

Dhir, Halliday, Sutherland. UK Survey of Dioxins and Furans in Construction Products.