Queensland University of Technology School of Physical and Chemical Sciences Analysis of alternative water sources for use in the manufacture of concrete This thesis is submitted as partial fulfilment of the requirements for the degree of Maters of Applied Science By Leigh M McCarthy B.Sc Supervisor: Dr Serge Kokot Assoc Supervisor: Prof Ray L Frost Abstract In Australia and many other countries worldwide, water used in the manufacture of concrete must be potable At present, it is currently thought that concrete properties are highly influenced by the water type used and its proportion in the concrete mix, but actually there is little knowledge of the effects of different, alternative water sources used in concrete mix design Therefore, the identification of the level and nature of contamination in available water sources and their subsequent influence on concrete properties is becoming increasingly important Of most interest, is the recycled washout water currently used by batch plants as mixing water for concrete Recycled washout water is the water used onsite for a variety of purposes, including washing of truck agitator bowls, wetting down of aggregate and run off This report presents current information on the quality of concrete mixing water in terms of mandatory limits and guidelines on impurities as well as investigating the impact of recycled washout water on concrete performance It also explores new sources of recycled water in terms of their quality and suitability for use in concrete production The complete recycling of washout water has been considered for use in concrete mixing plants because of the great benefit in terms of reducing the cost of waste disposal cost and environmental conservation The objective of this study was to investigate the effects of using washout water on the properties of fresh and hardened concrete This was carried out by utilizing a 10 week sampling program from three representative sites across South East Queensland The sample sites chosen represented a cross-section of plant recycling methods, from most effective to least effective The washout water samples collected from each site were then analysed in accordance with Standards Association of Australia AS/NZS 5667.1 :1998 These tests revealed that, compared with tap water, the washout water was higher in alkalinity, pH, and total dissolved solids content However, washout water with a total dissolved solids content of less than 6% could be used in the production of concrete with acceptable strength and durability These results were then interpreted using chemometric techniques of Principal Component Analysis, SIMCA and the Multi-Criteria Decision Making methods PROMETHEE and GAIA were used to rank the samples from cleanest to unclean It was found that even the simplest purifying processes provided water suitable for the manufacture of concrete form wash out water These results were compared to a series of alternative water sources The water sources included treated effluent, sea water and dam water and were subject to the same testing parameters as the reference set Analysis of these results also found that despite having higher levels of both organic and inorganic properties, the waters complied with the parameter thresholds given in the American Standard Test Method (ASTM) C913-08 All of the alternative sources were found to be suitable sources of water for the manufacture of plain concrete Statement of Originality The work contained in this thesis has not been previously submitted to meet requirements for an award at this or any other higher education institution To the best of my knowledge and belief, the thesis contains no material previously published or written by another person except where due reference is made Signature _ Leigh M McCarthy Date _ Acknowledgements This project would not have been possible without the support of many people Many thanks to Dr Serge Kokot and Prof Ray Frost for their direction, assistance, and guidance In particular my supervisor, Dr Serge Kokot, who read my numerous revisions and helped make some sense of the confusion Thanks are also due to Mr Glenn Carson, Dr Dak Bakewash and Mr Russel Gutsky from Readymix for their assistance and for providing me with the financial means to complete this project I would also like to thank Dr Wayde Martens whose help was integral in the completion of this thesis Also thanks to my fellow postgraduate students, who sympathized with my complaints, understood my frustrations and most of all offered guidance and support And finally, thanks go to my family and friends who endured this long process with me, always offering support and love Thanks to my parents who were unwavering in their encouragement and support and who, through years of patience and hard work afforded me a sense of ambition and self, allowing me to reach for my goals To my sister Clare thanks for your patience, understanding and tolerance of my disappointments and for sharing my triumphs Lastly, to my brother Sean whose own achievements served as a reminder that only your best effort will Table of Contents Introduction 12 1.1 Prologue 12 1.2 Concrete and its constituents 15 1.3 Cement and aggregates 17 1.3.1 Hydration reactions of cement 21 1.3.2 Cement Hydration Products 23 1.3.3 Admixtures 25 1.4 Water Quality, its properties and influence on concrete 26 Methodology 29 2.1 Sample Guidelines 29 2.2 Sample Preparation 29 2.3 Equipment and Materials 31 2.4 Chemical Preservatives 31 2.5 Sampling Methods and Procedures 31 2.6 Preparation of Concrete Cylinders 33 2.7 Instrumental Analysis 34 2.8 Instrumentation used for the analysis of water samples 35 2.8.1 Measurement of pH 35 2.8.2 Measurement of Relative Alkalinity 36 2.8.3 Measurement of Electrical Conductivity 37 2.8.4 Measurement of Total Dissolved Solids 38 2.8.5 Measurement of Chloride 39 2.8.6 Compressive strength Analysis of concrete samples 40 2.9 Multi Criteria Decision Making Methods 42 2.9.1 2.10 Chemometric Analysis 42 Multicriteria Decision Making (MCDM) 51 2.10.1 Preference Ranking Organisation Method for Enrichment Evaluation (PROMETHEE) 52 2.10.2 Compilation of baseline data for water quality 55 3.1 Washout Waters – Building a baseline 55 3.2 Concrete Plant sites throughout SE-Qld 56 3.2.1 Southport Concrete Plant 56 3.2.2 Beenleigh Concrete Plant 56 3.2.3 Murarrie Concrete Plant 56 3.3 Analysis of Baseline Water 58 3.4 Simple Analysis of Baseline Water Sample Results 58 3.5 Chemometric interpretation of Water Quality data 62 3.6 Chemometric Analysis of Baseline Samples 66 3.6.1 Principal Component Analysis 66 3.6.2 PROMETHEE and GAIA 72 3.7 Geometric Analysis for Interactive Aid (GAIA) 54 Chapter Summary 80 Analysis of Alternative Water Sources for Comparison 81 4.1 Location of alternative water source sampling sites 81 4.2 Southport Sea Water 83 4.2.1 Southport Treated Effluent 83 4.2.2 Kawana Treated Effluent 83 4.2.3 Coolum Bore Water 83 4.2.4 Gympie Bore water 84 4.2.5 Ipswich River Water 84 4.2.6 Murarrie Bore Water 84 4.2.7 Coomera Dam Water 84 4.2.8 Coomera Bore water 84 4.3 Analysis of Alternative Water Sources 86 4.4 Analysis according to water type 88 4.4.1 Sea Water 88 4.4.2 Treated Effluent 89 4.4.3 Bore Water 91 4.4.4 Dam and River Water 91 4.5 Chemometric analysis of alternative water source samples 93 4.5.1 PCA analysis 93 4.5.2 SIMCA 97 4.5.3 Fuzzy Clustering 103 4.5.4 PROMETHEE and GAIA 105 4.6 Chapter Summary 116 Concluding Remarks 117 References 119 Table of figures Figure 2.1 Testing Apparatus used to determine Compressive Strength 40 Figure 2.2 Example of Principal Component Analysis 46 Figure 3.1 Biplot with baseline sample results with IRMV and compressive strength results67 Figure 3.2 PCA Biplot of PC1 vs PC2 with all variables including compressive strength results 69 Figure 3.3 GAIA plot showing reference variables and baseline sample sites with compressive strength results 73 Figure 3.4 GAIA plot showing reference variables and baseline sample sites 77 Figure 4.1 PC1 v PC2 for alternative water source results 92 Figure 4.2 PC1 v PC2 all Alternative and all Baseline samples with compressive strength results 94 Figure 4.3 Cooman Plot For Murarrie and Coomera Dam including RSD values 100 Figure 4.4 Cooman Plot For Murarrie and Sea Water including RSD values 100 Figure 4.5 Plot of Discrimination power vs variables for Southport & Murarrie 106 Figure 4.6 GAIA plot for all Alternative and all Baseline samples 109 Figure 4.7 GAIA Plot for all Alternative and all Baseline samples with compressive strength results 114 10 Table 4.8 shows that 5cd outranks all the other objects with the highest value of  Therefore, 5cd is the water sample with the best quality overall It can also be seen that many objects that have positive values of  belong to the Coomera bore (cb) and Coomera dam (cd) locations followed by Gympie (g) and Ipswich (i) Both the Kawana (k) and (c) samples are interspersed with very similar indices This is not unexpected, as both samples are forms of treated effluent The Murarrie bore samples (mb) and Southport effluent (e) appear at the end of the better performing samples It can also be seen that 5m is outranked by all the other objects with the lowest value of  From the positioning of all sea water (sw) and the Murarrie (m) results throughout the PROMETHEE Net Ranking it can be said that they have the lowest ranking This finding supports the hypothesis that sea water would perform worst out of all of the alternative water sources due to its high level of salts Whilst Murarrie performed the worst, it should be noted, that, as discussed previously, all sampling sites produced water of sufficient quality to use in the manufacture of concrete Just as in the PROMETHEE Net Ranking of the baseline datasets, this Net Ranking highlights weeks 6m and 6b2 as outliers, whilst all water sources group together fairly well Of note is the difference between the last Murarrie value ( =-0.328, 7m) and first Coomera Bore sample value (= 0.136, 5cb), which suggests that they are well separated This same dataset was then interpreted with the aid of GAIA (Figure 4.6), and allows us to view the data in a 2-dimensional plane [2] Also, the pi axis shows the direction of the compromise resulting from the weights allocated to the criteria The alternatives are to be considered to locate in the direction of the pi axis [3] Figure 4.6 shows that the criteria pH and SO4 are grouped tightly as are Cl and TDS It can also be seen that RA is almost orthogonal to Cl indicating that RA is independent of Cl 110 111 Table 4.9 PROMETHEE Net Ranking for all Alternative and all Baseline samples with Compressive strength Results Where : (s) Southport, (m) Murarrie, (b) Beenleigh, (cd) Coomera Dam, (cb) Coomera Bore, (sw) sea water, (e) Effluent, (mb) Murarrie Bore, (i) Ipswich, (g) Gympie, (c) Coomera Numbers represent the sample week eg: 1s is the first sample from Southport 112 Analysis of figure 4.6 shows that sw objects have high negative score on PC1 and the cd objects have high positive scores on the same PC Both Murarrie (m) and the seawater (sw) objects are not clean but the relative uniformity of the sw characteristics as opposed to that of m samples is quite evident by the scatter of the m group The Southport (s) objects are mostly grouped with low negative scores on PC1 and the remainder of the alternative water objects are distributed with positive scores on this PC Considering the direction and the length of the decision axis, 5cd is preferred to all the other objects, supporting the findings from the PROMETHEE Net Ranking In order to confirm the findings of these PROMETHEE and GAIA analysis plots, the same interpretation methods were applied to a second data matrix, containing compressive strength results The new matrix contained 90 object by variables The PROMETHEE Net Ranking order shows the full ranking of the 90 objects according to the value of the net ranking index () (Table 4.9) Once again, it can be seen that the Coomera dam (cd) samples perform best as a group while the Murarrie (m) and Sea water (sw) samples appear to be the least clean Interestingly, there appear to be no significant changes in the Net Ranking Order of the objects This confirms the earlier hypothesis that compressive strength results appear to be independent of each of the other variables This PROMETHEE analysis tends to follow the same ranking order of the baseline sets, where 6m appears as an outlier Each of the rest of the sample groups rank closely as there were no outside influences changing the composition of the water dramatically This PROMETHEE analysis supports the PCA results obtained in Section 4.5.1 Here, Figure 4.2, with the exception of sw, did not show any clear separation of the groups from each other, indicating that they are all very similar in composition, making it hard for the PCA to differentiate between the sample groups 113 Figure 4.7 GAIA Plot for all Alternative and all Baseline samples with compressive strength results Where : (s) Southport, (m) Murarrie, (b) Beenleigh, (cd) Coomera Dam, (cb) Coomera Bore, (sw) sea water, (e) Effluent, (mb) Murarrie Bore, (i) Ipswich, (g) Gympie, (c) Coomera Numbers represent the sample week eg: 1s is the first sample from Southport 114 Once again, GAIA was applied to the same data matrix, allowing us to view the data in a 2dimensional plane [2] Once again, Figure 4.7 shows that the criteria pH and SO4 are grouped tightly as are Cl and TDS It can also be seen that RA is almost orthogonal to both the and 28 day compressive strength results, indicating that RA is independent of these variables The objects are distributed similarly on the Figure 4.6 Considering the direction and the length of the decision axis, 5cd is preferred to all the others, supporting the findings from the PROMETHEE Net Ranking Also of note, is the close proximity of 6m to sample 5cd, which were identified in the PROMETHEE analysis (Table 4.9) as being the best performers It can also be seen that 6s and 6b samples, which were also affected by influx of potable water, appear away from their source group and closer the cd sample group, indicating their increased cleanliness This GAIA plot also identifies sw samples as an outlier group, as was found in the PCA analysis (Figure 4.2) However, whilst the PCA did not differentiate clearly between the sample groups, this plot shows clearly defined sample groups, even though they are similar in nature, i.e Figure 4.7 highlights the specific groupings of the baseline samples and their separation from the alternative samples This is interesting as it reinforces the hypothesis that while the baseline samples are clearly separated into three groups, the groups themselves are not altogether dissimilar 115 4.6 Chapter Summary Water samples collected at nine different alternative water sampling source sites were analysed to assess their quality on the basis of the Industry Standard Readymix Monitoring Variables Subsequently, concrete cylinders were made with the use of these waters and tested for crush MPa The analysis of these alternative water sources was carried out following the exact same procedures as those used to analyse the baseline data to ensure comparability Analysis of the multivariate data matrix of the crush properties and water quality with the use of PCA indicated that the water quality does not seriously affect the performance of the concrete provided that the water lies within the specified limits The quality of the waters was ranked on the basis of their multivariate variables and subsequently compared to the baseline relative ranking scale This facilitated the new ranking system in which Coomera performed the best, and sea water performed worst Each of the alternative water sources did not appear to have detrimental effects on concrete properties and as such appear to be a practicable means of reducing the need for fresh potable water in concrete manufacture 116 Concluding Remarks All water sources commonly contain a wide range of dissolved chemicals and suspended solids One of the cleanest types of water, potable water still contains a number of both chemical and physical impurities Thus, as this type of water is currently the only acceptable source for the manufacture of concrete, it is possible that other water sources containing similar levels of impurities are also suitable for concrete production However, in order to ensure that no detrimental effects are experienced, each alternative water must be subject to a series of tests and meet acceptable industry standards in regard to both the physical and chemical characteristics of the concrete [10, 57, 124] The aims and objectives (Section 1.1) were addressed by focusing on the effects of impurities in mixing water on concrete performance as well as constructing a baseline for acceptable threshold limits This study effectively assessed the use of recycled washout water as well as a range of alternative water sources for use in concrete manufacture Analysis of the water sources currently in use in South East Queensland was conducted first, enabling the construction of a baseline to which all alternative water sources could then be compared Throughout this study, each of the baseline water samples as well as the alternative water samples, were subject to testing to determine their adherence to the acceptable limits for impurities in the mixing water, (Table 3.1), and then subjected to and 28 day compressive strength testing Subsequent analysis of the results indicated that the water quality does not seriously affect the performance of the concrete provided that the water lies within the specified limits This study found that concrete manufactured with washout water appears to have minimal detrimental effects and is a feasible means of reducing wash water as a waste product by allowing its reuse in subsequent batches These results were based on the performance requirements of National Standards on concrete mixing water including recycled water [9, 10, 54, 56, 57, 124] 117 After the completion of the baseline threshold limits, the information collected through a series of elemental, physico-chemical and structural testing was then interpreted successfully using chemometric modelling Each of the three baseline water sites were clearly ranked according to cleanliness using PROMETHEE analysis However, the separation between each group was small, indicating that all water sources were within the acceptable threshold limits, although some conditions applied (eg seawater only suitable for use in plain concrete) The quality of the waters was ranked on the basis of their multivariate variables and a baseline relative order was obtained that can be applied on any other water samples for comparative purposes in the future Based on the experimental work carried out during this study, the suitability of other nonpotable water sources was able to be assessed This study found that whilst the limits provided in AS1379 and ASTM C94 are specific for potable water, much larger impurity concentrations can be tolerated, i.e, generally, water contaminated with industrial wastes and alternative reclaimed waters, are acceptable water sources for the manufacture of concrete This investigation into the chemical composition of each water source, as well as the physical properties such as compressive strength, allowed the identification of key elements, variables and characteristics There is not sufficient research in the area of alternative, reclaimed water sources to compile specific limits for each impurity tested here However, this study found that when new sources of water are identified, provided they are tested for their effects on strength development of a standard concrete mix compared to the same mix prepared with potable tap water, and no adverse effects identified, the 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Originality The