ALCOA OF AUSTRALIA No. 37 EVALUATING TECHNIQUES FOR REDUCING pH OF BAUXITE PROCESSING RESIDUE SAND AT DEPTH USING GYPSUM AND IRRIGATION I. R. Phillips August 2010 ISSN 1320-4807 1 SUMMARY This report presents findings from a three year study that was established to identify the role of irrigation in residue rehabilitation, and whether depth of gypsum placement affects rehabilitation performance. Irrigation did not significantly improve rehabilitation performance nor did it significantly affect the movement of gypsum throughout the residue sand profile. This was because irrigation was not applied on a continuous basis, but when residue sand water storage decreased to a value considered low enough to induce drought stress in the vegetation cover. Although some movement of gypsum to depths below its zone of incorporation was detected, the rate of movement was relatively slow, and incomplete removal of carbonate was still evident two years after incorporation. It was suggested that restricted movement may be due to the low solubility of gypsum coupled with the poor water retention properties of residue sand. Changes in Na, CO3 and HCO3 proved to be more reliable indicators of gypsum interaction with residue sand than pH, Ca and SO 4. If shallow gypsum incorporation was to be recommended, additional studies would need to confirm that its rate of movement throughout the residue sand profile was faster than the rate of plant root growth. This would identify whether gypsum movement was a limiting factor to plant root growth, hence water and nutrient uptake. Irrigation was found to significantly increase above-ground biomass (as measured by cover) but had no affect on species richness. Plant performance was found to be independent of gypsum incorporation depth. This was because both the shallow and deep treatments resulted in gypsum being distributed throughout much of the plant root zone. As such, neither the shallow or deep gypsum treatments should have limited plant root distributions in terms of their accessibility to moisture and nutrients. The higher bulk density, coupled with the hostile chemical characteristics, of residue sand below the zone of gypsum incorporation was considered to pose the greater restriction to depth of root penetration. Plant roots were also observed to be associated with high concentrations of gypsum, particularly in the shallow treatments. It is possible that plant roots in shallow gypsum treatments may preferentially remain closer to the surface, which may also render plants more susceptible to drought stress during summer. It is recommended that: Irrigation be removed from the current prescription for residue rehabilitation because it (1) is not a sustainable practice in terms of long term management of residue disposal areas, (2) is 2 an inefficient use of a limited natural resource at a time when water management is essential, and (3) may restrict root distribution to shallow depths in the residue sand profile. Deep gypsum incorporation be retained as the preferred method due to its proven effectiveness in rapidly altering the characteristics of residue sand such that it is more conducive for plant growth, and it encourages deeper penetration of plant roots. Maintain botanical monitoring of the trials to test whether any of the treatments causes a reduction in rehabilitation performance in the longer term. Use the parameters Na, CO3 and HCO3 in conjunction with Ca, SO4 and pH as a measure of gypsum interaction with residue sand. Prior to establishing any field trial, ensure that a complete history of past management is obtained and assess whether any previous activity will affect the primary objectives (or hypotheses to be tested) of the study. INTRODUCTION Developing and refining effective methods for improving the growth media for rehabilitating Alcoa of Australia (Alcoa) bauxite-processing storage areas (RSA) represent a primary objective of residue rehabilitation research. Maximising plant-root distribution throughout the residue sand profile is considered critical to establishing and maintaining a sustainable vegetation cover across RSA embankments. The incorporation of gypsum to reduce alkalinity and pH, and the use of irrigation to increase plant-water availability throughout the profile and to leach soluble salts from the plant-root zone, represent two key steps in residue rehabilitation to encourage root penetration to depth, and to increase the volume of residue sand utilised by the plant rhizosphere. In 2003, Alcoa’s Western Australian Operations (WAO) altered the depth and rate of gypsum incorporation into residue sand from a shallow application of 50 t/ha (disced to a 300 mm depth) to 225 t/ha incorporated throughout a depth of 1500 mm. Gypsum incorporation to depth is expensive (increased from $10,000/ha to $14,500/ha in 2006), and alternative methods of distributing gypsum throughout the profile have been considered. These have included the use of a ripping tine (Phillips 2010b), and leaching surface-applied gypsum with irrigation and/or rainfall (Eastham and Mullins 2004b). The study by Eastham and Mullins (2004b) suggested that a shallow application of 225 t/ha resulted in rapid leaching of gypsum through the residue sand profile with a corresponding reduction in pH at depth (> 600 mm) 15 months after application. 3 Up until 2008, irrigation had routinely been installed at all new rehabilitated residue sand embankments to assist with plant establishment. It is impractical to maintain irrigation in the longterm; however, rehabilitation protocol currently does not include a strategy to gradually remove the vegetation’s irrigation-dependency. Furthermore, there is concern that irrigated vegetation will not achieve the required root structure to survive without artificial water additions, particularly over summer, and the vegetation cover will be at a density which can only be sustained by continued watering. Eastham and Morald (2004a) found that root density in 1 and 2 year old residue rehabilitation tended to be highest in the surface 300 mm and decreased rapidly with depth. Furthermore, total root biomass was observed to decrease significantly with increasing compaction of residue sand. Recent work has found that the surface 300 mm of the residue sand profile dries out to very low water contents (<0.03 m3/m3) during summer, and that compaction increases markedly below the zone of gypsum incorporation (Dobrowolski et al. 2009). A better understanding of plant-water relations is therefore required to determine if (1) a sustainable vegetation cover can be established without irrigation, (2) the vegetation cover has a root structure and physiology capable of surviving under extreme water-stress conditions, and (3) the resulting cover density is acceptable from a visual amenity perspective. To address the above concerns, a field trial was established at the Kwinana and Pinjarra RSAs in 2005 (Kiepert 2005) to (1) compare the performance of rehabilitation on residue sand embankments receiving shallow and deep incorporation of 225 t/ha of gypsum, (2) determine if irrigation is necessary for plant establishment and survival, (3) determine if irrigation assists in leaching of gypsum to depth as a means of reducing residue profile pH and creating an environment encouraging root growth to depth, (4) evaluate the effect of irrigation on the root architecture of selected plant species, and (5) compare the visual perspective of non-irrigated and irrigated rehabilitated embankments due to sustainable vegetation cover density. To date, chemical analysis of residue sand profiles and botanical monitoring of the established vegetation have been undertaken on three occasions since commencement of the trial. Additionally, root distribution and microbial “health status” of selected rehabilitated areas of RSA were measured in 2007 (Dobrowolski et al. 2009). The primary objectives of this study are to present data on (1) the effect of leaching on gypsum distribution throughout the residue sand profile, and (2) the effect of irrigation on plant cover performance. Results from root distribution, chemical distributions within a residue sand profile to a depth of 3 m, and microbial “health status” at selected rehabilitated sites will also be provided to support conclusions based on the above two objectives. 4 MATERIALS AND METHODS Field Trial Description A detailed description of the trial can be found in Kiepert (2005) and Wilkinson (2005). A brief summary of this information is presented below. Trial establishment - Pinjarra The trial was established on RSA4 and RSA5 in 2005. The southern batter of RSA5 was mechanically placed in 1993 and 1996 where Block 1 treatments were created. Blocks 2 and 3 were created on the SW corner of RSA4, and residue sand in this area had been mechanically placed in 1994 and 1995. All three blocks were located on outer embankments that had previously received the standard shallow 50 t/ha of gypsum, fertiliser addition (poultry manure) and dust suppression crops. Thus, the effects of shallow gypsum addition as a treatment may not be evident. Each block comprised of a randomised plot design. Plots on RSA5 were 50 m wide by 60 m wide, and 50 m by 50 m on RSA4. Trial establishment - Kwinana Due to a lack of available space, the trial at Kwinana RSA was split across two areas. The irrigation component of the trial was established on Area F3, and the depth of gypsum incorporation was established on Areas F4 and F5. The irrigation trial (Area F3) was established on plots 70 m long by 17 m wide in an area that had been mechanically placed in 1996/1997, and had received fertilizers (poultry manure) and multiple gypsum applications to establish dust suppression crops. The gypsum trial (Area F4/5) comprised of a fully randomised treatment design incorporating plots 20 m long by 50 m wide. The trial was set-up on a residue sand outer embankment that had been hydraulically placed in 2004 (i.e. 6 months old). Prior to commencement of the trial, this area had only received surface bitumen and mulch for dust suppression. No gypsum or fertilizers had been applied prior to trial establishment. Gypsum Treatments Pinjarra Prior to shallow gypsum incorporation, all weeds were scrapped off to a depth of about 100 mm and discarded. However, where deep incorporation of gypsum was studied, all weeds were buried at a depth of about 1500 mm. For shallow gypsum incorporation treatments, 225 t/ha of gypsum were spread on the residue sand surface and disc harrowed to a depth of 200 mm, after which the surface was covered with bitumen for dust control. Each plot received a basal dressing of 2.571 t/ha of DAP5 based fertiliser (Appendix 1), which was incorporated by ripping to 600 mm. Since gypsum had been applied prior to fertiliser incorporation, it is highly likely that ripping re-distributed the gypsum throughout the 0 – 600 mm depth interval. This greater depth of incorporation will need to be accounted for when assessing the depth of gypsum leaching. Unfortunately, the shallow gypsum irrigated and non-irrigated plots received a higher rate of gypsum (300 t/ha) instead of 225 t/ha. Each plot received 1.88 kg/ha of seed, followed by 60 mm of mulch (equivalent to a surface application of 600 m3/ha), and planted out with about 3400 stems/ha. The seeded and planted species and quantities used are provided in Appendix 2 (Wilkinson 2005). Each planted seedling received a 50 grams fertiliser tablet (Appendix 1), and was marked with a bamboo cane to assist with differentiating between planted and seeded individuals. In each plot, 68 species were seeded and or planted; 18 species were planted only, 14 were seeded only and 36 were planted and seeded (Wilkinson 2005). Kwinana Trials were set-up as described above for Pinjarra, and all plots received the correct amount of gypsum (i.e. 225 t/ha). Irrigation Treatments The method of irrigation was the same at both Kwinana and Pinjarra. Water was supplied along rows of aluminium pipes (12 m apart) with riser sprinklers every 9 m of length. Each sprinkler had an effective radius of about 9 m, resulting in some areas receiving 2 to 3 times more water than others. The sprinkler system was constructed such that there was 20 m distance between the irrigated and nonirrigated areas. Irrigation commenced on 21st December 2005, the day before the botanical monitoring was completed. Thus, irrigation was not included as a treatment in data analysis for data collected before December 2005 as it would not have affected plant germination or growth, or gypsum leaching. Irrigation scheduling was based on a water balance approach (G. Mullins, personal communication). During the 2005/2006 summer, irrigated plots received 20.4 mm per day for seven irrigation events. During the 2006/2007 summer the irrigated plots received 42.7 mm per day for three irrigation events. 6 Sampling of Residue Sand Profiles Pre-gypsum addition (April 2005) Prior to gypsum incorporation, samples of residue sand at all plots (except the deep gypsum, no irrigation treatment at Pinjarra) were collected at depths of 100, 300, 500, 700, 900, 1100, 1300 and 1500 mm for chemical analyses. Samples were obtained by hand-augering, stored in sealable plastic bags, and transported to CSBP Ltd for chemical analysis. Prior to analysis, each sample was air-dried and passed through a 2 mm sieve. The < 2 mm fraction was retained for analysis. Each sample was analysed for available (2M KCl) nitrate (NO3) and ammonium (NH4), Colwell (0.5 M NaHCO3 pH 8.5) phosphorus (P), Colwell (0.5 M NaHCO3 pH 8.5) potassium (K), available (0.25 M KCl) sulphur (S), organic carbon (Org C, Walkley Black), amorphous iron (am-Fe, ammonium oxalate), electrical conductivity (EC, 1:5 residue sand to water ratio), pH (H2O and 0.01 M CaCl2, 1:5 residue sand to solution ratio), exchangeable (0.1M BaCl2/0.1M NH4Cl) calcium (Ca), magnesium (Mg), sodium (Na) and potassium (K) (Appendix 3 and 4). Post-gypsum addition (November 2005) Post-gypsum sampling of each plot was undertaken in November 2005. Each plot was sampled (n = 2) at three random locations at depths of 0 – 100, 500 – 700 and 1300 – 1500 mm. Samples were collected and analysed as outlined above. The non-consistent sampling depths between sampling events limits the extent of statistical analysis that can be undertaken (Appendix 3 and 4). 6-month sampling (May 2006) Additional sampling of residue sand profiles was undertaken 6-months after gypsum incorporation (i.e. May 2006). Samples were collected only from those treatments receiving “a shallow application of 225 t/ha and no irrigation” for the following reasons. Firstly, this treatment provided the highest gypsum concentration in the smallest volume of residue sand, thereby providing the best opportunity to detect gypsum leaching throughout the profile. Secondly, this treatment provided the opportunity to monitor gypsum leaching via rainfall infiltration alone, which would reflect conditions should irrigation be removed from standard rehabilitation operations. Samples were collected from the 0 – 800 mm depth interval as follows. Sampling locations (n = 2) in each plot were selected randomly; one from the upper section, the other from the lower section, of the embankment. A PVC pipe (50 mm i.d. 900 mm long) was carefully hammered into the residue sand to a depth of 800 mm. The pipe was then dug out and both ends sealed with a PVC end cap. Each 7 sealed pipe was retained in a vertical position prior to extruding the residue sand core in 100 mm increments. Each increment of residue sand was placed in a clearly identifiable, sealable plastic bag, and transported to CSBP Ltd for chemical analysis. Each sample was analysed for the parameters listed above, with the addition of amorphous Al (am-Al, ammonium oxalate) and exchangeable Al (1M KCl). Amorphous Al represents a significant adsorption surface for P, and contributes significantly to the surface charge characteristics of residue sand (Phillips and Chen 2010). Exchangeable Al (which includes soluble and weakly-sorbed forms of Al) is known to vary with pH, and so may represent a major cation balancing the surface electrical charge carried by residue sand. 12-month sampling (December 2006) Sampling of the “non-irrigated plots with a shallow gypsum incorporation of 225t/ha of gypsum” was repeated after winter to determine if infiltrating rainwater has caused leaching of gypsum to depths below the zone of incorporation (i.e. > 600 mm). Cores of residue sand to a depth of 800 mm were collected as outlined above. Previous sampling events highlighted the difficulty in detecting statistically significant differences between specific samples based on solid phase concentrations. Changes in solution phase concentrations are known to be more reliable measures of treatment effects on soil chemistry (Phillips and Bond 1989). Consequently, the water-soluble and solid phase concentrations of a range of parameters were measured for each sample as follows. A saturated paste was prepared by mixing a known mass of residue sand with Mill-Q deionised water until saturation characteristics were attained (θsat ≈ 0.3). The paste was left overnight to equilibrate, and a sample of the pore-water removed under vacuum. The pore-water was analysed for Ca, Mg, K, Na, Al, pH, EC, P, Cl, SO4, NH4, NO3, HCO3 and CO3 using standard techniques (Rayment and Higginson 1992). The remaining solids were sub-sampled and analysed for the parameters listed above, and for EDTAextractable copper (Cu), zinc (Zn), manganese (Mn) and Fe, exchangeable Fe, phosphorus buffering index (PBI), Total Fe and Total Al. All analyses were performed by CSBP Ltd. Botanical Monitoring Botanical monitoring has been undertaken on three occasions since trial establishment; December 2005 (Wilkinson 2005), July 2006 (Narducci 2006) and August 2007 (LeRoy 2007) as follows. Three botanical monitoring plots were set-up within each treatment plot (Figure 1); (a) two 36 m2 (6 for density and cover of seeded and planted species, and (b) one 400 m2 (20 8 20 m or 10 6 m) 40 m) for density and survival of planted seedlings. At both RSAs, one of the 36 m2 plots was placed on the upper slope and one was placed on the lower slope, thereby allowing position on the slope to be included in data analyses. For the KW irrigation trial, the treatment plots were not wide enough for upper and lower plots to be meaningful so the two monitoring plots were treated as replicates (pseudo replicates). An aluminium tag marked with a permanent plot number and a fence dropper was used to mark the north-west corner of each monitoring plot and wooden stakes were used to mark the remaining plot corners (Figure 1). A more detailed description of individual plot locations can be found in Wilkinson (2005). Germination success A quadrat (2 2 m) was laid within the 36 m² monitoring plots, and the number and percent cover (of the 4 m² area) of each species recorded. Planted seedlings were recorded separately from germinated seed. This process was repeated until the entire 36 m² plot had been monitored (i.e. 9 quadrats per 36 m² plot). A single plant within a 36 m² plot is equivalent to 278 plants/ha (10,000 m² 36 m²), assuming even distribution of the plants. Therefore, the density of a species required in the field to ensure that it occurs within the monitoring plot is at least 278 plants/ha. However, given the way seed is applied during rehabilitation (hand-seeding with preferential segregation of seeds of different mass), an even distribution of seed is highly unlikely. In fact, groups of plants of the same species can often be observed in the field. Planted success The number of each planted species was recorded in a 400 m² area. As the density of many planted species was low, large monitoring plots were used to increase the reliability of the data. Each plant was identified, the bamboo cane moved as close as possible to the base of the plant, and fluorescent paint sprayed on the top of the cane to indicate it had been counted. If the plant was dead, the death was recorded and the cane was removed. For the Kwinana Irrigation Trial there were three monitoring plots (RD117, RD123 and RD129) which contained large pipes close to, or exposed at, the soil surface. As these areas may not have received gypsum and the pipe may affect plant growth, they were not included in the calculations for the plots. The approximate area affected by the pipes was measured and subtracted from the plot area, the bamboo stakes were removed and the reduced area was taken into account for species density calculations. A single plant within a 400 m² area is equivalent to 25 plants/ha (10,000 m² 400 m²), assuming even distribution of the plants. Therefore, the density of a species required to ensure that it is monitored in our plots is at least 25 plants/ha. 9 Data Analyses Residue sand Statistical differences between residue sand characteristics were analysed at discrete depths using ANOVAs and LSD All-Pairwise Comparisons Tests. Data for the two sites was analysed separately due to the difference in past history of gypsum and fertiliser at Pinjarra but not at Kwinana (depth of gypsum incorporation site). Botanical monitoring Summary data for each site was determined by averaging the density and cover data for all monitoring plots regardless of treatment. Irrigation trial plots were analysed separately from gypsum trial plots. Density, cover and number of species (species richness) were summed across species for each 36 m² monitoring plot, and this number was used to compare treatments. Data was analysed using Statistix 8.0 using ANOVAs and LSD All-Pairwise Comparisons Tests. Data for the two sites, Kwinana and Pinjarra, was analysed separately to determine site differences. RESULTS AND DISCUSSION – RESIDUE SAND Effect of Time on Gypsum Leaching In Residue Sand Profiles Water Inputs Over The Period Of Study The amounts of rainfall ± irrigation added over the four sampling events are presented in Figure 2. Irrigated treatments received significantly more water (p <0.05) than unirrigated treatments, and this was most obvious over the December 2005 to June 2006 period (Event 2). Both the non-irrigated and irrigated treatments received the same amount of water over events 1 and 3 since irrigation was not applied over the winter period. Over the monitoring period (August 2005 to December 2007), Kwinana received significantly more water (p <0.05) than Pinjarra (i.e. 1869 mm versus 1808 mm). 2005 Sampling: Pre- and Post- Gypsum Incorporation - Pinjarra Gypsum addition, either via shallow or deep incorporation, generally increased exchangeable Ca, available-S, and EC, and decreased pH, relative to residue sand characteristics prior to gypsum addition (Figure 3). The magnitude of these changes was more pronounced in the shallow gypsum treatments. Changes in exchangeable Na, bicarbonate-K and bicarbonate-P concentrations were less obvious, which may be due to previous fertiliser and gypsum additions as part of RSA5’s rehabilitation management history. Generally, nutrient concentrations, pH and EC for irrigated treatments were found to be similar in magnitude to those for non-irrigated treatments. However, this finding was not consistent throughout the trial. 10 A primary objective of this trial was to determine if shallow incorporation (0 – 300 mm) of high rates of gypsum and subsequent leaching, could improve subsoil characteristics that promote root growth to depth. The parameters initially considered to demonstrate this effect best are pH, EC, exchangeable Ca, exchangeable Na and available-S (Figure 3). Prior to gypsum incorporation, (Figure 3), values of pH, EC, exchangeable Ca, exchangeable Na and available-S in the 0 – 100, 500 – 700 and 1300 – 1500 mm depth intervals was 7.8, 9.0 and 9.2; 57, 7 and 9 mS/m; 5.5, 4.3 and 4.1 cmol/kg; 0.1, 0.1 and 0.6 cmol/kg; and 602, 10 and 9 mg/kg, respectively. For post-gypsum incorporation, values of pH, EC, exchangeable Ca, exchangeable Na and available-S in the 0 – 100, 500 – 700 and 1300 – 1500 mm depth intervals was 7.4, 8.3 and 8.4; 138, 26 and 32 mS/m; 10.5, 4.6 and 4.4 cmol/kg; 0.1, 0.3 and 0.8 cmol/kg; and 3043, 200 and 233 mg/kg, respectively. These data suggest that in the shallow gypsum incorporation treatment, much of the gypsum still remains in the surface layer (0 - 100 mm), although some penetration to depth (up to 1500 mm) may have occurred. 2005 Sampling: Pre- and Post- Gypsum Incorporation - Kwinana Gypsum addition, either via shallow or deep incorporation, generally increased exchangeable Ca, available-S, and EC, and decreased pH and exchangeable Na, relative to residue sand characteristics prior to gypsum addition (Figure 4). The magnitudes of these changes were more pronounced in the shallow gypsum treatments. Changes in bicarbonate-K and bicarbonate-P were less obvious, particularly in the deep gypsum treatments. Prior to gypsum incorporation (Figure 4), values of pH, EC, exchangeable Ca, exchangeable Na and available-S in the 0 – 100, 500 – 700 and 1300 – 1500 mm depth intervals were 9.8, 10.1 and 10.1; 48, 94 and 104 mS/m; 3.0, 2.6 and 2.4 cmol/kg; 3.7, 5.9 and 5.7 cmol/kg; and 10, 21 and 25 mg/kg, respectively. Following gypsum incorporation, values of pH, EC, exchangeable Ca, exchangeable Na and available-S in the 0 – 100, 500 – 700 and 1300 – 1500 mm depth intervals were 8.0, 9.0 and 9.0; 163, 50 and 103 mS/m; 9.9, 4.0 and 5.6 cmol/kg; 0.6, 2.4 and 3.5; and 2965, 357 and 594 mg/kg, respectively. These data are consistent with that from the Pinjarra trial, and suggest that following shallow gypsum incorporation, the majority of gypsum still remains in the surface layer (0 - 100 mm), although some penetration to depth (up to 1500 mm) may have occurred. 2006 Sampling: 6-Month and 12-Month - Pinjarra Additional sampling at times of 6-months and 12-months following gypsum incorporation were undertaken to better understand if gypsum leaching to depth within the residue sand profile has 11 occurred. Sampling was restricted to only those shallow gypsum plots receiving no irrigation for reasons outlined earlier. For clarity, only the data for those ions (i.e. Ca, Na and SO4) and parameters (i.e. pH and EC) indicative of the presence of gypsum will be discussed in this report. Data for all other analyses undertaken are provided in Appendix 5. The distribution of pH within the residue sand profile tended towards lower values with increasing time (Figure 5). For example, the pH of the 0 – 100 mm depth for the pre-gypsum, post-gypsum, 6month and 12 month samplings was 7.8, 7.4, 7.1 and 6.9 respectively, while the pH of the 600 – 700 mm depth for the pre-, post- gypsum, 6-month and 12 month samplings was 9.0, 8.3, 8.7 and 6.8 respectively. After 12 months, the pH remained relatively constant at pH 7 over the 0 – 800 mm interval. A similar trend was observed for the EC. Exchangeable Ca and Na tended to demonstrate relatively small non-significant changes throughout the profile. Available SO4 did not display any significant variation throughout the profile with time. Distributions of water-soluble Ca, Na, SO4, CO3 and HCO3 are presented in Figure 6. Very little Ca and SO4 were found in the soil solution below a gypsum incorporation depth of 600 mm. There appeared to be a good relationship between the distribution of soluble and exchangeable Na with depth and pH at the 12-month sampling event. This relationship suggests that Na and its accompanying anion may be largely responsible for controlling the pH of residue sand. 2006 Sampling: 6-Month and 12-Month - Kwinana The pH of residue sand over the 0 – 800 mm depth decreased with time, although the changes over the 12-month period were small relative to values immediately following gypsum incorporation (Figure 5). For example, the pH of the 0 – 100 mm depth for the pre-gypsum, post-gypsum, 6-month and 12 month samplings was 9.8, 8.0, 8.3 and 7.6 respectively, while the pH of the 600 – 700 mm depth for the pre-gypsum, post-gypsum, 6-month and 12 month samplings was 10.1, 9.0, 9.8 and 8.7 respectively. In contrast to Pinjarra, however, the pH was observed to increase steadily over the 0 – 800 mm depth, and mimicked values observed immediately post-gypsum incorporation. The EC decreased significantly (p < 0.05) between the 6-month and 12-month sampling events in the 0 – 300 mm zone, and remained relatively constant at 10 mS/m below this depth. Exchangeable Ca and available SO4 tended to demonstrate relatively small non-significant changes throughout the profile. In contrast, exchangeable Na concentrations tended to decrease with increasing time within the 0 – 800 mm depth. 12 Water-soluble Ca and SO4 concentrations within the 0 – 800 mm depth were typically low relative to that in the adsorbed phase (Figure 6). The distribution of water-soluble Na concentrations displayed a similar pattern to that observed for pH. General Discussion Of the two sites at which the study was conducted, Kwinana provided the best opportunity to assess the effects of gypsum incorporation depth and subsequent leaching. This is because the depth of gypsum incorporation study was established at the only area which had not received previous gypsum and/or fertiliser additions. Although data interpretation for both sites was complicated by the absence of sampling immediately following gypsum and fertiliser addition (which may have highlighted the effect of gypsum on various chemical properties), previous fertiliser additions at the Pinjarra study area appear to have already resulted in a build-up of plant nutrients in the residue sand profiles. Therefore, gypsum and/or fertiliser from past additions could not be separated from that applied at the commencement of the trial, which limited an assessment of whether the non-irrigated and irrigated treatments have had a positive or otherwise impact on gypsum and nutrient availability and movement in residue sand profiles. The effects of gypsum on plant nutrient (N, P, K, Mg, Ca and S) concentrations and pH observed at Kwinana were not unexpected based on the known behaviour of gypsum in residue sand (Phillips 2010a). In general, these can be summarised as follows. The movement of gypsum throughout the residue sand profile will primarily be governed by its rate of dissolution, hence solubility in the porewater. The dissolution of gypsum is described as: CaSO4.2H2O ↔ Ca2+ + SO42- + 2H2O (CaSO4 log Ksp = - 4.58) (1) The solubility product (Ksp) of gypsum used in residue rehabilitation is about 0.22 g/100 mL (Phillips 2010a). This implies that when the concentration of gypsum in the pore-water is less than 0.22 g/100 mL, Eqn (1) will proceed to the right and dissolution of gypsum should occur. Whereas if pore-water gypsum concentrations exceed 0.22 g/100 mL, then Eqn (1) proceeds to the left and gypsum precipitation would occur. Due to the high application rates (particularly in the shallow incorporation treatment) and low solubility of gypsum, coupled with poor water retention properties of residue sand, considerable amounts of applied gypsum could persist in the residue sand for extended periods of time. In fact, excavations in the shallow incorporation trial found exceedingly high amounts of undissolved gypsum within the 0 – 200 mm depth, with some locations exhibiting nearly 100% 13 gypsum (i.e. no residue sand) in the 0 – 150 mm zone (Figure 7). The impacts of this dominance of gypsum on plant establishment and nutrient availability are currently unknown, although preliminary root distribution studies (see below) suggest this may in fact restrict root penetration depths. The ability of gypsum to alter the chemical properties of residue sand below the zone of gypsum incorporation must be considered limited, at least in the short term. Prior to gypsum amendment, residue sand typically contains very high concentrations of carbonate (about 18000 mg CO3 /L), with lower concentrations of bicarbonate (about 600 mg HCO3 /L), anions (Appendix 6). Following gypsum amendment, the concentration of these anions are considerably reduced (through formation of CaCO3 and conversion of CO3 to HCO3 as a function of pH (Stumm and Morgan 1981), with HCO3 becoming the dominant inorganic carbon-based ion (about 590 mg HCO3 /L; Appendix 6).The reduction in pH following gypsum addition arises from the reaction of Ca2+ with carbonate (CO32-) to form weakly-soluble CaCO3 (Barrow 1982): CaSO4 + Na2CO3 ↔ CaCO3 + Na2SO4 (CaCO3 log Ksp = - 8.48; Na2SO4 log Ksp = 0.7) (2) The smaller Ksp for CaCO3 compared to Na2SO4 results in CaCO3 being precipitated within the residue sand, with the more soluble Na2SO4 being leached from the material with drainage water. However, as soluble Ca moves with the leaching water, the opportunity for Na:Ca cation exchange reactions can also occur. Residue sand has a cation exchange capacity (CEC) of about 5 cmol/kg, and this is initially dominated by exchangeable Na. The dissolution of gypsum (Eqn 1) provides Ca in the water phase which can subsequently displace Na from the exchange sites according to: 2X-Na+ + Sol-Ca2+ ↔ X-Ca + 2Sol-Na2+ (3) where X refers to exchangeable cation and Sol refers to solution cation. As solution Ca concentrations decrease due to precipitation (Eqn 2) and cation exchange (Eqn 3), this would stimulate further dissolution of gypsum until the saturation index became zero, after which the Ca, SO4, Na, pH and EC of the solution phase would remain relatively constant. Over the period August to November 2005, the cumulative rainfall plus irrigation was ≈ 300 mm for both sites (Figure 2). If it is assumed that field capacity of residue sand is 0.2 cm3/cm3, then the depth of water movement can be conservatively estimated to be about 300÷0.2 = 1500 mm. Since the depth of shallow gypsum incorporation was up to 600 mm, sufficient water appears to have been applied to 14 the treatment plots to cause movement of gypsum to depths of up to 1500 mm. In fact, the depth of penetration of the wetting front from an individual irrigation event of 20 mm can potentially exceed 1200 mm (Figure 8). Changes in exchangeable Ca, exchangeable Na, available-S, EC and pH profiles were consistent with gypsum interaction with residue sand. For example, exchangeable Na concentrations in the 0 – 100, 500 – 700 and 1300 – 1500 mm depth intervals pre- and post- gypsum incorporation were 3.7, 5.9 and 5.7, and 0.6, 2.4 and 3.5, respectively. These changes may be a result of Ca:Na exchange as soluble Ca moves through the residue sand profile with drainage water (particularly in the surface layer) and leaching of readily-soluble Na. This suggests that shallow gypsum incorporation may be capable of altering the chemical composition of residue sand profiles, albeit at a much slower rate relative to deep incorporation. Based on the chemical composition of gypsum (CaSO4), the presence of Ca and/or SO4 below the zone of gypsum incorporation should be a good indicator of gypsum leaching. Typically, the sorption characteristics of these two ions in the presence of hydrous Fe and Al oxides can limit their availability and mobility (Theng 1980; Cichota et al. 2007). Consequently, the combined effects of low gypsum solubility and strong sorption of the dissolution products (coupled with the formation of low solubility CaCO3), may be a major cause for only small (and possibly non-significant) changes in the concentration of Ca and/or SO4 in both the soluble and adsorbed phases. As mentioned above, non-gypsum amended residue sand is dominated by Na2CO3 and NaHCO3 (Appendix 6), whereas after gypsum amendment, the concentration of these anions are considerably reduced through formation of CaCO3 and conversion of CO3 to HCO3 as a function of pH. Thus, the relative proportion of water-soluble CO3 to HCO3 may provide a more reliable indicator of gypsum interaction with residue sand and mobility. For the Pinjarra study, no CO3 was present within the 0 – 800 mm depth, although HCO3 was present at a relatively constant concentration of 300 – 400 mg/L (Figure 6). Although this suggests gypsum leaching has occurred below the depth of incorporation (about 600 mm), there is a strong possibility this movement may be a consequence of previous gypsum additions (i.e. prior to trial establishment). In contrast, the Kwinana study demonstrated watersoluble CO3 concentrations about 1% of that found in unamended residue sand (about 200 mg/L) were present at depths below 400 mm (Figure 6). Since the Kwinana trial was established on an embankment which had not previously received gypsum and fertilizer additions, this finding suggests some gypsum leaching below the depth of incorporation (about 600 mm) may have occurred. Unfortunately, the limited sampling depth of 0 – 800 mm does not provide information on how the CO3 to HCO3 ratio varies at greater depths which may have indicated the depth of gypsum penetration 15 since trial commencement. Alternately, CO3 concentrations may have decreased naturally over time due to leaching and/or carbonation by infiltrating water (Phillips 2010a). In 2008, samples of residue sand were collected from a 4-year old rehabilitated residue sand embankment to a depth of 3 m, and were analysed for a range of chemical and physical parameters (Phillips, unpublished data). Parameters relevant to gypsum leaching are provided in Appendix 6b. Gypsum was incorporated to a depth of up to 1.5 m, and key indicators such as pH, Ca, Na (in both the solid and soluble fractions), and soluble SO4, CO3 and HCO3, indicate that the effects of gypsum were primarily confined to its depth of incorporation (1 – 1.5 m). These data provide strong evidence that little movement below the zone of incorporation has occurred within a 4 year period. Thus, leaching of surface-applied gypsum would not appear to be suitable for ameliorating the pH of residue sand at depth. Previous studies (Phillips 2010a) suggested that Ca preferentially reacts with CO3 (Eqn 1) prior to undergoing cation exchange. Calcium sorption involves both adsorption and precipitation reactions but the relative importance of these two mechanisms in removing solution Ca was not studied in this experiment. Wong and Ho (1995) reported that Na was preferentially adsorbed by residue mud relative to Ca at solution cation fractions > 10%, and that Ca rarely exceeded 20% of the exchange phase. This cation exchange behaviour can be attributed to the presence of zeolitic-type minerals grouped as desilication product (DSP; Wong and Ho 1995). Desilication product (DSP) is formed by the reaction of soda and alumina with reactive silica during the Bayer process. Residue mud contains about 11% DSP, whereas residue sand contains about 1% DSP. Phillips (2010a) estimated that DSP may account for up to 3 cmol/kg of charge, or ≈ 40% of the overall CEC. This implies that a significant proportion of the CEC of residue sand may exhibit a relatively low affinity for Ca (particularly at high solution Ca fractions) and this would encourage Ca to remain in solution and be preferentially lost via precipitation as CaCO3. Additional Information Plant root distribution Field studies on root distribution for three plant species, Hardenbergia comptoniana, Acacia cochlearis and Eucalyptus gomphocephala were selected to represent examples of ground cover, shrub and tree species, respectively (Dobrowolski et al. 2009). It was generally found that irrespective of plant species, the roots were primarily confined to the zone of gypsum incorporation. Also, compaction within the residue sand profile increased dramatically below the zone of gypsum 16 incorporation. This appeared to restrict root penetration below the gypsum zone, which was particularly evident for the shallow gypsum treatment. This restriction would severely limit the volume of residue sand available to the plant for extracting water and nutrients, which may markedly affect the long term sustainability of the plant cover system. The apparent dependency of depth of root penetration on depth of gypsum incorporation provides strong support for not recommending shallow gypsum incorporation for residue rehabilitation. Health criteria The soil microbial biomass is mainly composed of fungi and bacteria, and provides an indication of short-term changes in soil fertility. The fungi and bacteria present in residue sand would be largely responsible for the decomposition of plant residues, and they can release plant nutrients via mineralisation, or can accumulate nutrients through immobilisation within the microbial biomass. To assess the fertility status of the residue sand at the Pinjarra site, residue sand from the 300 (within root zone), 1000 (below root zone) and 1800 (compaction zone) mm depths were analysed for microbial biomass. All samples recorded negligible microbial biomass and would be regarded as exhibiting low fertility (Dobrowolski et al. 2009). Although these findings are not directly related to the objectives of this study, they do highlight the need to improve the fertility status and nutrient-supplying capacity of the overall residue sand profile as a means of encouraging greater plant root distribution. Without this ability to supply nutrients, plant roots may be restricted to zones of artificial nutrient sources such as that created by gypsum incorporation and/or fertiliser addition. Conclusions and Recommendations Shallow and deep gypsum incorporation improved the chemical characteristics of residue sand for plant growth, although these effects were less obvious in profiles which had a previous history of gypsum and/or fertiliser additions. Gypsum addition typically reduced pH and Na concentrations, and increased Ca and SO4 concentrations within the zone of incorporation. Some gypsum leaching below the zone of incorporation was evident, but shallow incorporation may limit amelioration of unfavourable chemical conditions at depth due to the limited solubility of gypsum in residue sand. The extent of leaching was however better described using water-soluble CO3 to HCO3 ratios. Shallow gypsum incorporation represents a significant cost-saving in operational residue rehabilitation. However, based on (1) issues associated with solubility and in-situ movement within the residue sand profile, and (2) possible limitations on plant root distribution, this method of 17 incorporation is not recommended as part of the operational prescription of residue rehabilitation. It is recommended that the current method of deep incorporation be maintained. RESULTS AND DISCUSSION – BOTANICAL MONITORING A detailed description of the botanical monitoring component of this study was prepared by LeRoy (2007). A summary of those findings are provided in this report. Irrigation Trial - Pinjarra Irrigation did not affect cover or species richness of natives and exotics (p >0.05). However, density was significantly greater in non-irrigated plots than irrigated plots (p <0.05), which was largely due to the contribution from exotics (Figures 9, 10 and 11). Native species contributed to a significantly greater amount of cover and species richness relative to the exotic species (p <0.001) despite exotics having a significantly greater density measurement than natives (p<0.001). Over the 2005 – 2007 monitoring period, the proportion of cover increased significantly with each consecutive year (p<0.001). Plant density in 2006 and 2007 was significantly greater than in 2005 (p <0.001), whereas species richness was significantly greater in 2005 and 2006 than in 2007 (p <0.05). Visually, rehabilitation in Block 1 appeared to be out-performing that in Blocks 2 and 3. Block 1 contained less exotic species and therefore looked healthier (Figures 12 and 13). Analyses of results showed Block 1 had significantly less density than Blocks 2 and 3 (p <0.05), as well as significantly less species richness (p <0.05). This may be due to the exotic plants in Blocks 2 and 3 contributing to the higher density and species richness. Vegetation on the upper slope appeared to be less healthy than vegetation at the bottom of the slope. Although the upper slope of the plots exhibited a higher cover, density and species richness than the lower slope, these differences were not statistically significant (p >0.05). The history of RSA5 embankment construction revealed that the upper section was hydraulically poured whilst the lower section was mechanically constructed. It is possible that this difference in embankment construction may have contributed to differences in plant performance (mechanically constructed tend to be compacted); however, any compaction should have been relieved during trial establishment and gypsum incorporation. Moisture profiles within the plant root zone (<2 m) did not exhibit major differences in between upper slope and lower slope locations, particularly during the late-summer period (Phillips unpublished data). However, plant water use (based on plant transpiration data over 2009; Phillips unpublished data) appeared to be greater on the lower than upper slopes. Other factors 18 contributing to the performance of vegetation located on the upper part of the embankment may also involve operational activities at the adjacent mudlake (e.g. exposed to alkaline spray from mud/sand pipe discharge and/or alkaline dust). Irrigation Trial - Kwinana Irrigated plots displayed a significantly greater cover by natives and exotics (p <0.05) yet significantly less density than non-irrigated plots (p <0.05). Species richness was not significantly affected by irrigation (p >0.05) (Figure 14, 15 and 16). There was no significant difference in proportion of cover between native and exotic species (p >0.05). The density of exotic species was significantly greater (p <0.001) than that of natives, irrespective of irrigation treatment. In contrast, exotic plants exhibited significantly less species richness compared with native species (p <0.001). Over the three monitoring periods, species richness of natives numbered 21 compared to 7 for exotic species. Over the three-year monitoring period, cover increased significantly with each consecutive year (p <0.001) (Figure 14). The density of plants was significantly greater in 2007 than in 2005 and 2006 (p <0.001). Species richness was greatest in 2005, but this number decreased significantly in 2006 and 2007 (Figure 16). Gypsum Trial - Pinjarra There were no significant differences (p >0.05) in cover, density and species richness for natives and exotics growing in shallow and deep gypsum treatments (Figures 17, 18, 19). Also, there were no significant differences (p >0.05) in vegetation cover and density between position on the embankment (i.e. upper or lower). However, species richness was significantly greater on the upper slope than the lower slope (p <0.001). Block 1 exhibited significantly less cover than Blocks 2 and 3 (p <0.05) and significantly less density than Block 3 (p <0.05). Blocks 1, 2 and 3 were all significantly different from each other with respect to species richness, with Block 1 having the least number of species and Block 3 the most (p <0.001). Native plants displayed significantly greater species richness than exotic plants (p <0.001), but significantly less density (p <0.001). There was no significant difference between the proportion of cover for exotic and native species (p >0.05) (Figure 17, 18 and 19). 19 Over the three-year monitoring period, cover was found to significantly increase on an annual basis (p <0.001). Plant density increased significantly from 2005 to 2006, but species richness declined significantly in 2007 relative to that in 2006 (p <0.001). Gypsum Trial - Kwinana There was no significant difference between shallow and deep gypsum treatments with respect to vegetation density, cover and species richness of natives and exotics (p >0.05). There was however a significant difference between the density, cover and species richness of native and exotic species. Native species displayed significantly greater cover and species richness (p <0.001), yet significantly less density (p <0.05) than exotic species (Figures 20, 21 and 22). Vegetation cover and density significantly increased over the 2006 – 2007 period relative to that observed in 2005 (p <0.001 and p <0.05 respectively). In contrast, species richness significantly declined in 2007 compared to that in 2005 and 2006 (p <0.001). Position of vegetation on the embankment (upper or lower slope) had no significant effect on cover, density or species richness of native and exotic species (p >0.05). Discussion and Conclusions Irrigation trial Plant density was found to be significantly lower in irrigated plots compared with non-irrigated plots. This was associated with a lower density of exotic species in irrigated plots than non-irrigated plots. It is possible that the additional water provided by irrigation may have accelerated growth of the native vegetation, thereby crowding out exotic species. This is supported from the finding that exotics have proliferated in non-irrigated plots. Furthermore, irrigation did not improve species richness at either site. From the monitoring data, amounts of irrigation based on soil-water deficits have not been found to provide any significant benefit to residue rehabilitation. To achieve any significant benefits, much greater and more frequent irrigation applications may be required. However, this is not practical from a water resource perspective, and if a sustainable vegetation cover is to be achieved. During the summer of 2006/2007 many species became stressed and some senesced (LeRoy 2007). Despite this, many species recovered after early winter rain periods, with many plants producing new growth. This provides additional support for removing irrigation from operational residue 20 rehabilitation prescription; however, continued monitoring of species performance will be undertaken to ensure that rehabilitation failure will not occur in future years. An additional finding from this study has been identification of those species that cannot survive under non-irrigated conditions (LeRoy 2007). These data are being used to refine the current rehabilitation seed mix. Gypsum trial Depth of gypsum incorporation in residue rehabilitation did not affect the measurement indices cover, species richness or density. Based on plant performance alone, it could be concluded that plant performance is independent of gypsum incorporation depth. But it must be remembered that the majority of plant roots resided in the surface 0 – 300 mm which was well within the depth of gypsum incorporation for both gypsum treatments. CONCLUSIONS AND RECOMMENDATIONS Conclusions This report presents findings from a three year study to identify the role of irrigation in residue rehabilitation, and whether depth of gypsum placement affects rehabilitation performance. The chemical analysis of residue sand profiles at varying times after gypsum incorporation suggested some movement of gypsum to depths below its zone of incorporation, and that the rate of movement was relatively slow. This rate of movement may be related to the low solubility of gypsum and the poor water retention properties of residue sand. Importantly, changes in Na, CO3 and HCO3 proved to be more reliable indicators of gypsum interaction with residue sand than pH, Ca and SO4. This was because the strong sorption (adsorption and/or precipitation) of Ca and SO4 tended to reduce their concentrations in solution to very low concentrations. If shallow gypsum incorporation were to be recommended, studies would need to confirm that its rate of movement throughout the residue sand profile was faster than the rate of plant root growth. This study would need to ensure that gypsum movement was not a limiting factor to plant root growth, hence water and nutrient uptake. Irrigation did not significantly improve rehabilitation performance. These findings are not unexpected because irrigation was not applied on a continuous basis, rather when plant-stress from water-deficit in residue sand storage was estimated. Although irrigated plots received significantly more water than non-irrigated plots, the additional water probably was of little benefit to the plant cover due to the rapid hydraulic conductivity of residue sand (≈ 20 m/d). 21 Botanical monitoring found that a major response to irrigation was higher above-ground biomass (as measured by cover) but no difference in species richness. Plant performance was also found to be independent of gypsum incorporation depth. The combined effect of this would be that operational prescription for residue rehabilitation would involve the removal of irrigation and inclusion of shallow incorporation of gypsum. Although the removal of irrigation would not be expected to significantly hinder plant performance, shallow gypsum incorporation is not recommended for the following reasons. Firstly, shallow incorporation should have been restricted to a depth of 0 – 300 mm; however, the actual depth was most likely 0 – 600 mm. Secondly, independent root distribution studies showed that a very high proportion of roots reside in the 0 – 300 mm with only a few roots penetrating to greater depths (Dobrowolski et al. 2009). Therefore, both the shallow and deep gypsum treatments resulted in gypsum being distributed throughout the root zone. As such, neither the shallow or deep gypsum treatments would have hindered plant root distributions and their accessibility to moisture and nutrients due to hostile chemical characteristics of the residue sand. Also, plant roots were observed to be associated with high concentrations of gypsum, particularly in the shallow treatments. Gypsum may provide a less-hostile environment for plant roots due to its lower pH, high nutritional value and potentially higher water content by virtue of its finer texture, compared to residue sand. It is possible therefore that plant roots in shallow gypsum treatments may preferentially remain closer to the surface with gypsum. Unfortunately this may also render plants more susceptible to drought stress during summer. Recommendations Although this study has provided good information on the reaction of gypsum with residue sand, factors such as past gypsum and fertiliser additions, incorporation of gypsum throughout the root zone irrespective of gypsum treatment, and irrigation applications which did not markedly affect plant available water, may not have truly tested the effect of gypsum placement and irrigation on plant performance. Despite this, it is recommended that: Irrigation be removed from the current prescription for residue rehabilitation because (1) it is not a sustainable practice in terms of long term management of residue disposal areas, (2) is an inefficient use of a limited natural resource at a time when water management is essential, and (3) may restrict root distribution to shallow depths in the residue sand profile. 22 Deep gypsum incorporation be retained as the preferred method because (1) its proven effectiveness in rapidly altering the characteristics of residue sand such that it is more conducive for plant growth, and (2) it encourages deeper penetration of plant roots. Maintain botanical monitoring of the trials to test whether any of the treatments causes a reduction in rehabilitation performance in the longer term. Use the parameters Na, CO3 and HCO3 in conjunction with Ca, SO4 and pH as a measure of gypsum interaction with residue sand. Prior to establishing any field trial, ensure that a complete history of past management is obtained and assess whether any previous activity will affect the primary objectives (or hypotheses to be tested) of the study. REFERENCES Barrow NJ (1982) Possibility of using caustic residue from bauxite for improving the chemical and physical properties of sandy soils. Australian Journal of Agricultural Research 33, 275-285 Cichota R, Vogeler I, Bolan N, Clothier B (2007) Simultaneous adsorption of calcium and sulfate and its effect on their movement. Soil Science Society of America Journal 71, 703 – 710 Dobrowolski MP, Mullins RG, Phillips IR (2009) Factors affecting plant root distribution in sand embankments of bauxite residue disposal areas. (Environmental Department Research Note No. 29 Alcoa of Australia: Perth) Eastham J, Morald T (2004a) Improving root penetration and vegetation growth on bauxite residue embankments. (Unpublished Report Alcoa Western Australia Engineering Operations Alcoa of Australia: Perth) Eastham J, Mullins G (2004b) Evaluating techniques for reducing pH of bauxite residue at depth using gypsum. (Unpublished Report Alcoa Western Australia Engineering Operations Alcoa of Australia: Perth) Keipert N (2005) Chemical properties of residue prior to application of gypsum and irrigation treatments. (Unpublished Report Environmental Department Alcoa of Australia: Perth) LeRoy M (2007) The effect of gypsum depth and irrigation on plant growth in residue sand. (Unpublished Report Environmental Department Alcoa of Australia: Perth) Narducci M (2006) Effect of irrigation on survival and growth of rehabilitation on residue embankments. (Unpublished Report Environmental Department Alcoa of Australia: Perth) Phillips IR (2010a) Characteristics of gypsum and fertiliser used in residue rehabilitation. (Environmental Department Research Note No. 35 Alcoa of Australia: Perth) 23 Phillips IR (2010b) Comparing techniques for incorporating gypsum into residue sand embankments at Alcoa’s residue disposal areas. (Environmental Department Research Note No. 32 Alcoa of Australia: Perth) Phillips IR, Bond WJ (1989) An extraction procedure for determining solution and exchangeable ions on the same soil sample. Soil Science Society of America Journal 53, 1294 – 1297 Phillips IR, Chen C (2010) Surface charge properties and sorption properties of bauxite-processing residue sand. Australian Journal of Soil Research 48, 77-87 Rayment GE, Higginson FR (1992) “Australian laboratory handbook of soil and water chemical methods”. (Inkata Press: Melbourne) Stumm W, Morgan JJ (1981) “Aquatic chemistry. 2nd edition”. (John Wiley & Sons: Brisbane) Theng BKG (1980) “Soils with variable charge”. (New Zealand Society of Soil Science: Lower Hutt New Zealand) Wilkinson C (2005) Botanical monitoring of gypsum/irrigation trials on bauxite residue – December 2005. (Unpublished Report Environmental Department Alcoa of Australia: Perth) Wong JWC, Ho GE (1995) Cation exchange behaviour of bauxite refining residues from Western Australia. Journal of Environmental Quality 24, 461- 466 24 Figure 1. A diagram (not to scale) of the botanical monitoring plots set up within each treatment plot. Distances for the different plots and compass bearings are shown. The dark square (■) is the Northwest corner of the plot and is marked in the field by a fence dropper and a permanent plot number Treatment plot area 20 m, 90º N 36 m² 20 m, 180º 28.28 m, 135º Down slope 400 m² 6m 6m 8.48 m 36 m² 25 Figure 2. Rainfall ± irrigation received over each residue sand sampling event (1 = August 2005 to November 2005; 2 = December 2005 to June 2006; 3 = July 2006 to December 2006; 4 = January 2007 to December 2007) 1000 KW -I PJ -I KW +I PJ +I Water Input Per Sampling Event (mm) 800 600 400 200 0 1 2 Sampling Event 3 26 4 pH (1:5 soil:water) 6 (a) 8 10 12 0 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr Depth (mm) 400 800 1200 1600 pH (1:5 soil:water) 6 (b) 8 10 0 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 400 Depth (mm) 12 800 1200 1600 27 EC (mS/m 1:5 soil:water) 0 (a) 40 80 120 160 200 0 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr Depth (mm) 400 800 1200 1600 EC (mS/m 1:5 soil:water) 0 (b) 40 80 120 160 0 Depth (mm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 28 200 Exch Ca (cmol/kg) 0 (a) 4 8 12 0 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr Depth (mm) 400 800 1200 1600 Exch Ca (cmol/kg) 0 (b) 4 8 12 0 Depth (cm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 29 Exch Na (cmol/kg) 0.0 (a) 0.2 0.4 0.6 0.8 1.0 0 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr Depth (mm) 400 800 1200 1600 Exch Na (cmol/kg) 0.0 (b) 0.2 0.4 0.6 0.8 1.0 0 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr Depth (mm) 400 800 1200 1600 30 Avail S (mg/kg) 0 (a) 1000 2000 3000 4000 0 Depth (mm) 400 800 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 Avail S (mg/kg) 0 (b) 1000 2000 3000 4000 0 Depth (mm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 31 Bicarb K (mg/kg) 0 (a) 20 40 60 80 100 120 0 Depth (mm) 400 800 Deep Gypsum 1200 Pre -Irr Pre +Irr Post -Irr Post +Irr 1600 Bicarb K (mg/kg) 0 (b) 40 80 120 0 Depth (mm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 32 Bicarb P (mg/kg) 0 (a) 40 80 120 160 200 0 Depth (mm) 400 800 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 Bicarb P (mg/kg) 0 (b) 40 80 120 160 200 0 Depth (mm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 Figure 3. Pinjarra gypsum irrigation trial – effects of (a) deep or (b) shallow gypsum incorporation on the vertical distribution of pH, EC, exchangeable Ca, exchangeable Na, available S, available K and available P. Values presented are for pre- and post- gypsum incorporation, and minus and plus irrigation 33 pH (1:5 soil:water) 6 (a) 8 10 12 0 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr Depth (mm) 400 800 1200 1600 pH (1:5 soil:water) 6 (b) 8 10 0 Depth (mm) 400 800 Shallow Gypsum 1200 Pre -Irr Pre +Irr Post -Irr Post +Irr 1600 34 12 EC (mS/m 1:5 soil:water) 0 (a) 40 80 120 160 200 0 Depth (mm) 400 800 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 EC (mS/m 1:5 soil:water) 0 (b) 40 80 120 200 0 400 Depth (mm) 160 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 800 1200 1600 35 Exch Ca (cmol/kg) 0 (a) 4 8 12 0 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr Depth (mm) 400 800 1200 1600 Exch Ca (cmol/kg) 0 (b) 4 8 12 0 Depth (cm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 36 Exch Na (cmol/kg) 0 (a) 2 4 6 8 0 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr Depth (mm) 400 800 1200 1600 Exch Na (cmol/kg) 0 (b) 2 4 0 Depth (mm) 400 800 1200 1600 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 37 6 8 Avail S (mg/kg) 0 (a) 1000 2000 3000 4000 0 Depth (mm) 400 800 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 Avail S (mg/kg) 0 (b) 1000 2000 3000 4000 0 Depth (mm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 38 Bicarb K (mg/kg) 0 (a) 20 40 60 80 100 0 Depth (mm) 400 800 Deep Gypsum 1200 Pre -Irr Pre +Irr Post -Irr Post +Irr 1600 Bicarb K (mg/kg) 0 (b) 40 80 120 0 Depth (mm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 39 Bicarb P (mg/kg) 0 (a) 40 80 120 160 200 0 Depth (mm) 400 800 Deep Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 Bicarb P (mg/kg) 0 (b) 40 80 120 160 200 0 Depth (mm) 400 800 Shallow Gypsum Pre -Irr Pre +Irr Post -Irr Post +Irr 1200 1600 Figure 4. Kwinana gypsum irrigation trial – effects of (a) deep or (b) shallow gypsum incorporation on the vertical distribution of pH, EC, exchangeable Ca, exchangeable Na, available S, available K and available P. Values presented are for pre- and post- gypsum incorporation, and minus and plus irrigation. 40 Exchangeable Na (cmol/kg) Exchangeable Ca (cmol/kg) 0 (a) 20 40 0 60 (b) 0 4 6 0 40 80 Depth (cm) 40 Depth (cm) 2 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 80 120 160 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 Exchangeable Na (cmol/kg) Exchangeable Ca (cmol/kg) 0 20 40 0 60 (d) (c) 0 2 4 6 0 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 40 Depth (cm) Depth (cm) 40 80 120 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 80 120 160 160 41 pH (water) 6 (a) 7 8 9 EC (mS/m) 10 0 11 (b) 0 Depth (cm) 80 120 160 200 0 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 EC (mS/m) pH (water) 6 7 8 9 10 0 11 (d) (c) 0 40 80 120 160 200 0 40 Depth (cm) 40 Depth (cm) 120 120 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 80 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 120 160 80 40 40 Depth (cm) 40 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 42 Available SO4 (mg/kg) 0 (a) 2000 4000 6000 0 Depth (cm) 40 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 160 Available SO4 (mg/kg) 0 (b) 2000 4000 6000 0 Depth (cm) 40 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 160 Figure 5. Effect of time (pre- and post- (0, 6 and 12 months) after gypsum incorporation, on fertilizer and gypsum transport, and selected chemical properties. Values presented are for pre- and postshallow gypsum incorporation, and minus irrigation. For each set of 4 graphs, (a) and (b) refer to data for the Kwinana trial, and (c) and (d) refer to data for the Pinjarra trial. For available S, (a) refers to data for the Kwinana trial, and (b) refers 43 to data for the Pinjarra trial. Ca (cmol/kg) 0 (a) 5 10 15 20 25 0 Depth (cm) 20 40 Available Soluble 60 80 Ca (cmol/kg) 0 (b) 5 10 15 0 Depth (cm) 20 40 Available Soluble 60 80 44 20 25 Na (cmol/kg) 0 (a) 0.4 0.8 1.2 2 0 20 Depth (cm) 1.6 Available Soluble 40 60 80 Na (cmol/kg) 0 (b) 0.4 0.8 1.6 0 20 Depth (cm) 1.2 Available Soluble 40 60 80 45 2 SO4-S (mg/kg) 0 (a) 2000 4000 6000 0 Depth (cm) 20 40 Available Soluble 60 80 SO4-S (mg/kg) 0 (b) 2000 4000 0 Depth (cm) 20 40 Available Soluble 60 80 46 6000 CO3 and HCO3 (mg/L) 0 (a) 1000 2000 3000 0 HCO3 CO3 CO3 + HCO3 Depth (mm) 200 400 600 800 CO3 and HCO3 (mg/L) 0 (b) 100 200 300 400 500 0 HCO3 CO3 Depth (mm) 200 CO3 + HCO3 400 600 800 Figure 6. Vertical distribution of Ca, Na and SO4 in the water-soluble and solid (available phase) fractions, and soluble alkalinity, for residue sand 12 months after shallow gypsum incorporation. For each set of 2 graphs, (a) refers to data for the Kwinana trial, and (b) refers to data for the Pinjarra trial 47 (a) (b) Figure 7. (a) Large pieces of gypsum present within the residue sand profile, and (b) high concentrations of gypsum in the 0 – 200 mm depth interval at the shallow gypsum incorporation trial. 48 (b) 0.3 0.25 0.2 0.15 0.1 0.05 0 5 mm 100 mm 300 mm 600 mm Control 0 50 100 150 Time (hours) 200 250 Drainage Below 600 mm (% of applied) Volumetric Water Content (mm3/mm3) (a) 6 4 2 0 0 50 100 150 Time (hours) 200 250 Volumetric Water Content (mm3/mm3) (c) 0.3 0.25 10 mm 100 mm 300 mm 600 mm 1200 mm 1500 mm 0.2 0.15 0.1 0.05 0 0 50 100 150 Time (hours) 200 250 Figure 8. Simulated (HYDRUS-1D) water content at specific depths within the (a) 600 and (c) 1500 mm depth interval, and the amount of drainage following a single irrigation event 49 120 Cover (%) 100 80 2005 60 2006 2007 40 20 0 Natives +irr Exotics +irr Natives -irr Exotics -irr Figure 9. Comparison of cover of natives and exotics in irrigated and non-irrigated plots over 3 monitoring years at Pinjarra. 35 Density (plants/m2) 30 25 2005 20 2006 15 2007 10 5 0 Natives +irr Exotics +irr Natives -irr Exotics -irr Figure 10. Comparison of density of natives and exotics in irrigated and non-irrigated plots over 3 monitoring years at Pinjarra 35 Species Richness 30 25 2005 20 2006 15 2007 10 5 0 Natives +irr Exotics +irr Natives -irr Exotics -irr Figure 11. Comparison of species richness of natives and exotics in irrigated and non-irrigated plots over 3 monitoring years at Pinjarra 50 Figure 12. Rehabilitation in Block 1 at Pinjarra with few exotics Figure 13. Rehabilitation in Block 3 at Pinjarra showing a groundcover of exotic species including Medicago polymorpha and Lupinus cosentinii 51 60 50 Cover (%) 40 2005 30 2006 2007 20 10 0 Natives +irr Exotics +irr Natives -irr Exotics -irr Figure 14. Comparison of cover of natives and exotics in irrigated and non-irrigated plots over 3 monitoring years at Kwinana 25 Density (plants/m2) 20 15 2005 2006 2007 10 5 0 Natives +irr Exotics +irr Natives -irr Exotics -irr Figure 15. Comparison of density of natives and exotics in irrigated and non-irrigated plots over 3 monitoring years at Kwinana 30 Number of species 25 20 2005 15 2006 2007 10 5 0 Natives + irr Exotics + irr Natives - irr Exotics - irr Figure 16. Comparison of species richness of natives and exotics in irrigated and non-irrigated plots over 3 monitoring years at Kwinana 52 45 40 Density (plants/m2) 35 30 2005 25 2006 20 2007 15 10 5 0 Natives deep Exotics deep Natives surface Exotics surface Figure 17. Comparison of density of natives and exotics in surface and deep gypsum plots over 3 monitoring years at Pinjarra 80 70 Cover (%) 60 50 2005 40 2006 2007 30 20 10 0 Natives deep Exotics deep Natives surface Exotics surface Figure 18. Comparison of cover of natives and exotics in surface and deep gypsum plots over 3 monitoring years at Pinjarra 35 Number of Species 30 25 2005 20 2006 15 2007 10 5 0 Natives deep Exotics deep Natives surface Exotics surface Figure 19. Comparison of species richness of natives and exotics in surface and deep gypsum plots over 3 monitoring years at Pinjarra 53 14 Density (plants/m2) 12 10 2005 8 2006 6 2007 4 2 0 Natives deep Exotics deep Natives surface Exotics surface Figure 20. Comparison of density of natives and exotics in surface and deep gypsum plots over 3 monitoring years at Kwinana 40 35 Cover (%) 30 25 2005 20 2006 2007 15 10 5 0 Natives deep Exotics deep Natives surface Exotics surface Figure 23. Comparison of cover of natives and exotics in surface and deep gypsum plots over 3 monitoring years at Kwinana 45 40 Number of species 35 30 2005 25 2006 20 2007 15 10 5 0 Natives deep Exotics deep Natives surface Exotics surface Figure 24. Comparison of species richness of natives and exotics in surface and deep gypsum plots over 3 monitoring years at Kwinana 54 Appendix 1. Chemical composition of di-ammonium phosphate (DAP) fertiliser and tablets Chemical Composition of DAP Fertiliser Component Rate Active Element Rate DAP 1500kg/ha P = 300kg/ha N = 265kg/ha K2S04 (granulated) K= 300kg/ha CuS04 Cu = 10kg/ha ZnS04 (Granulated) Zn = 16kg/ha MgS04 Mg = 30kg/ha MnS04 (granulated) Mn = 15kg/ha NaMo Mo = 0.25kg/ha Boron (Granulated) B = 1.5kg/ha Chemical Composition of DAP Tablet (50 g) Total Nitrogen (N) Total Phosphorous (P) Total Potassium (K) Sulphur (S) Calcium (Ca) Chloride (Cl) Iron (Fe) Manganese (Mn) Copper (Cu) Zinc (Zn) Concentration 14.4% 16.0% 6.3% 1.1% 0.01% 5.7% 0.01% 1.3% 0.64% 0.34% 55 Appendix 2a. Summary of species used, whether they were planted and/or seeded and the quantity of seeds or planted seedlings used Species Spp code Planted/seeded Seeds used (g/ha) Pinjarra block 1 Acacia cochlearis Acacia Cyclops Acacia huegelii Acacia lasiocarpa Acacia pulchella Acacia rostellifera Acacia saligna Acacia truncate Agonis flexuosa Allocasuarina fraseriana Allocasuarina humilis Brachyscome iberidifolia Callitris preissii Calothamnus quadrifidus Carpobrotus virescens Conospermum triplinervum Conostylis aculeate Conostylis candicans Daviesia divaricata Daviesia nudiflora Dianella revolute Dichopogon capillipes Diplolaena dampiera Dodonaea aptera Dodonaea hackettiana Dryandra lindleyana Dryandra sessilis Eremophila glabra Eucalyptus decipiens Eucalyptus foecunda Eucalyptus gomphocephala Gompholobium tomentosum Grevillea crithmifolia Grevillea thelmanniana Guichenotia ledifolia Hakea lissocarpha ACACOC ACACYC ACAHUE ACALAS ACAPUL ACAROS ACASAL ACATRU AGOFLE ALLFRA ALLHUM BRAIBE CALPRE CALQUA CARVIR CONTRI CONACU CONCAN DAVDIV DAVNUD DIAREV DICCAP DIPDAM DODAPT DODHAC DRYLIN DRYSES EREGLA EUCDEC EUCFOE EUCGOM GOMTOM GRECRI GRETHE GUILED HAKLIS P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P S S S S 7.6 35.3 5.0 28.4 S S S S 15.1 1.0 46.0 1.7 S S S 14.8 51.0 17.7 S S S S 17.7 11.7 127.1 2.5 S S S S 45.4 5.0 3.1 10.1 S S S S 10.1 11.4 20.2 37.3 S 19.8 14 39 48 236 18 18 18 76 80 65 21 56 Planted (/ha) Pinjarra block Kwinana 2&3 Gypsum 14 14 39 39 48 48 237 236 18 18 18 18 19 18 77 76 80 80 66 65 21 21 Kwinana Irrigation 14 39 42 236 18 18 18 76 80 65 21 8 99 81 24 148 80 26 0 100 56 24 149 80 26 8 99 81 24 148 80 26 8 99 81 24 148 80 26 153 15 15 16 35 154 15 15 16 35 153 15 15 16 35 153 15 15 16 35 22 93 31 29 106 28 118 45 52 85 22 94 31 29 107 28 118 45 52 85 22 93 31 29 106 28 118 45 52 85 22 93 31 29 106 28 118 45 52 85 Species Spp code Planted/seeded Seeds used (g/ha) Pinjarra block 1 Planted (/ha) Pinjarra block Kwinana 2&3 Gypsum 19 19 113 112 Hakea prostrata HAKPRO P S 30.3 19 Hakea trifurcata HAKTRI P S 6.2 112 Hardenbergia comptoniana HARCOM S 201.9 Hovea pungens HOVPUN S 105.9 Isolepis nodosa ISONOD P S 20.2 181 182 Jacksonia furcellata JACFUR P S 22.7 24 25 Jacksonia sternbergiana JACSTE S 7.6 Kennedia prostrata KENPRO P S 201.6 13 0 Leucophyta brownii LEUBRO P 119 119 Macrozamia riedlei MACREI S 7600, 1250, 9660¹ Melaleuca acerosa MELACE P S 31.1 100 100 Melaleuca huegelii MELHUE S 12.6 Melaleuca lanceolata MELLAN P S 0.9 67 67 Melaleuca nesophila MELNES P 48 48 Melaleuca viminea MELVIM P 73 73 Myoporum insulare MYOINS P 60 60 Nemcia capitatum NEMCAP P 43 43 Olearia axillaris OLEAXI P S 25.2 74 74 Olearia rudis OLERUD P S 15.5 29 25 Petrophile serruriae PETSER S 12.6 Phyllanthus calycinus PHYCAL P S 151.4 56 57 Pimelea ferruginea PIMFER P 77 78 Podotheca gnaphalioides PODGNA S 20.2 Rhagodia baccata RHABAC P S 35.3 92 92 Scaevola crassifolia SCACRA P S 76.1 64 64 Sollya heterophylla SOLHET P S 151.4 57 57 Spyridium globulosum SPYGLO P S 7.7 49 49 Templetonia retusa TEMRET P S 15.1 18 18 Trachymene coerulea TRACOE S 50.5 Trymalium ledifolium TRYLED S 9.0 Viminaria juncea VIMJUN P S 7.6 19 19 Xanthorrhoea preissii XANPRE P S 116.0 145 145 ¹ A different quantity of Macrozamia riedlei seeds were planted at Pinjarra, Kwinana gypsum trial and Kwinana irrigation trial respectively. 57 Kwinana Irrigation 19 112 181 24 181 24 13 119 0 119 100 100 67 48 73 60 43 74 29 67 48 73 60 43 74 29 56 77 56 77 92 64 57 49 18 92 64 57 49 18 19 145 19 145 Appendix 2b. Location and treatments applied to each botanical monitoring plot Site Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Pinjarra Kwinana Kwinana Kwinana Kwinana Permanent plot number 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 Location Block RSA5 RSA5 RSA5 RSA5 RSA5 RSA5 RSA5 RSA5 RSA5 RSA5 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSA4 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 3 3 3 3 3 3 3 3 3 3 na na na na Treatment Gypsum Irrigation shallow shallow deep deep deep deep deep shallow shallow shallow deep deep shallow shallow shallow deep deep deep shallow shallow shallow deep deep deep deep deep shallow shallow shallow shallow shallow deep deep deep deep no no yes yes yes no no yes yes yes no no yes yes yes yes yes yes no no no no no no yes yes yes yes yes no no no no no no 58 Slope Easting Northing upper lower upper lower 397948 397951 398001 398006 397996 398054 398051 398110 398108 398101 397716 397706 397736 397743 397724 397756 397743 397748 397828 397821 397814 397886 397874 397872 397927 397933 397987 397981 397973 398144 398158 389486 389498 389506 389497 6388588 6388558 6388587 6388552 6388580 6388581 6388559 6388584 6388566 6388583 6387350 6387342 6387295 6387292 6387315 6387257 6387255 6387257 6387181 6387170 6387184 6387167 6387146 6387154 6387137 6387133 6387156 6387138 6387153 6387154 6387141 6435783 6435765 6435758 6435794 upper lower upper lower upper lower upper lower upper lower upper lower upper lower upper lower upper lower upper lower upper lower upper Peg position NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW NW A NW Plot 6x6 and 20x20m 6x6m 6x6m 6x6m 20x20m 6x6 and 20x20m 6x6m 6x6m 6x6m 20x20m 6x6m 6x6 and 20x20m 6x6m 6x6m 20x20m 6x6m 6x6m 20x20m 6x6m 6x6m 20x20m 6x6m 6x6m 20x20m 6x6 and 20x20m 6x6m 6x6m 6x6m 20x20m 6x6 and 20x20m 6x6m 6x6m 6x6m 10x40m 6x6m Site Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Kwinana Permanent plot number 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 Location Block RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF4/5 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 RSAF3 na na na na na na na na na na na na na na 1 1 1 1 1 1 2 2 2 2 2 2 3 3 3 3 3 3 Treatment Gypsum Irrigation deep deep shallow shallow shallow shallow shallow shallow shallow shallow shallow deep deep deep deep deep deep deep deep deep deep deep deep deep deep deep deep deep deep deep deep deep no no no no no no no no no no no no no no no no yes yes yes yes yes yes yes no no no yes yes yes no no no 59 Slope Easting Northing lower 389510 389516 389510 389517 389527 389519 389532 389545 389529 389546 389550 389546 389554 389564 390035 390050 390015 390081 390091 390076 390119 390132 390106 390161 390180 390148 390205 390213 390189 390247 390247 390228 6435783 6435773 6435826 6435799 6435802 6435825 6435816 6435798 6435840 6435831 6435818 6435858 6435849 6435837 6436313 6436345 6436323 6436381 6436403 6436377 6436435 6436452 6436422 6436489 6436511 6436481 6436547 6436554 6436527 6436599 6436615 6436592 upper lower upper lower upper lower upper lower na na na na na na na na na na na na na na na na na na Peg position NW A NW NW A NW NW A NW NW A NW NW A NW NW B NW NW B NW NW B NW NW B NW NW B NW NW B Plot 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m 6x6m 6x6m 10x40m Appendix 3. Chemical properties of residue sand pre- and post- gypsum incorporation for the Pinjarra site Pre-Gypsum Incorporation Treatment No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp No irrig + Shallow gyp Dept h (mm) NO3 NH4 BicarbP (mg/kg) BicarbK (mg/kg) Avail-S (mg/kg ) (mg/kg ) Ox-Fe EC pH pH Ex Ca Ex Mg Ex Na Ex K ECEC (mg/kg ) (mS/m ) (CaCl2 ) (H2O ) (cmol/kg ) (cmol/kg ) (cmol/kg ) (cmol/kg ) (cmol/kg ) 100 4.67 1.00 92.00 110.33 2.00 1.00 10.00 57.33 169.4 3 9.97 0.44 2574 26 7.63 8.23 4.87 0.16 0.17 0.21 5.41 3 300 0.15 3813 7 8.07 8.93 4.53 0.07 0.14 0.12 4.86 3 500 1.33 1.00 3.33 44.67 5.97 0.12 3373 7 8.10 9.07 4.32 0.05 0.24 0.09 4.70 5 700 1.33 1.00 3.67 33.67 6.50 0.11 3723 7 8.27 9.23 4.17 0.06 0.36 0.08 4.67 7 900 1.33 1.00 4.33 25.00 9.73 0.13 3354 8 8.30 9.30 4.17 0.06 0.51 0.05 4.78 10 110 0 130 0 150 0 100 1.33 1.00 4.00 16.67 13.27 0.17 3484 9 8.33 9.27 4.02 0.07 0.64 0.04 4.76 13 1.33 1.00 5.00 15.00 13.63 0.12 3948 10 8.30 9.23 3.74 0.07 0.62 0.03 4.46 13 2.00 1.00 4.67 22.67 10.10 0.21 3913 12 8.33 9.23 4.97 0.27 0.74 0.03 6.01 13 7.00 1.00 138.50 103.00 31.75 0.67 2211 10 7.50 8.10 5.05 0.49 0.15 0.20 5.88 3 300 1.50 1.00 31.50 102.00 4.30 0.14 3740 7 8.15 8.85 3.73 0.11 0.07 0.19 4.09 2 500 1.50 1.00 9.00 110.50 4.15 0.11 4325 7 8.10 9.00 4.32 0.07 0.12 0.20 4.71 2 700 1.50 1.00 9.00 87.50 2.80 0.10 3618 6 8.20 9.10 3.97 0.06 0.17 0.17 4.36 4 900 1.50 1.00 6.50 85.00 4.15 0.09 3372 8 8.25 9.20 3.84 0.07 0.38 0.13 4.42 8 110 0 130 0 150 0 100 1.50 1.00 8.50 36.00 3.65 0.13 3086 8 8.25 9.15 3.87 0.08 0.58 0.08 4.61 12 1.50 1.00 5.00 15.00 4.20 0.09 2594 8 8.30 9.25 3.91 0.11 0.61 0.02 4.65 13 1.50 1.00 6.50 15.00 3.80 0.12 3048 8 8.30 9.35 3.78 0.10 0.60 0.03 4.50 13 6.33 1.00 111.00 98.33 601.8 0 0.62 2277 57 7.30 7.77 5.52 0.20 0.10 0.17 5.99 2 (mg/kg ) Org C (%) 60 ES P (%) No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp 300 1.33 1.00 8.33 46.67 35.53 0.13 2998 12 8.03 8.87 4.65 0.06 0.21 0.11 5.02 4 500 1.33 1.00 7.00 85.33 12.40 0.13 3337 8 8.00 8.97 4.71 0.07 0.11 0.15 5.04 2 700 1.33 1.00 10.67 70.67 9.57 0.17 3482 7 8.10 9.03 4.26 0.08 0.09 0.13 4.57 2 900 1.33 1.00 5.33 31.67 10.13 0.12 3728 8 8.23 9.20 4.05 0.06 0.38 0.07 4.56 8 110 0 130 0 150 0 100 1.33 1.00 4.67 20.67 8.63 0.12 4227 9 8.27 9.20 4.12 0.07 0.51 0.04 4.74 10 1.33 1.00 6.33 15.00 34.70 0.16 4203 11 8.30 9.20 4.10 0.08 0.58 0.03 4.78 11 1.33 1.00 6.33 15.00 9.07 0.12 4310 9 8.30 9.23 4.10 0.11 0.61 0.02 4.85 12 6.33 1.00 93.00 91.33 63.97 0.57 3045 17 7.63 8.23 4.95 0.18 0.10 0.19 5.42 2 300 1.33 1.00 13.67 60.33 15.93 0.16 3850 8 8.03 8.97 4.70 0.07 0.07 0.11 4.95 1 500 1.33 1.00 4.00 68.00 15.97 0.11 3530 7 8.10 9.07 4.25 0.05 0.12 0.13 4.55 3 700 1.33 1.00 4.33 36.67 8.23 0.12 2759 6 8.30 9.27 4.22 0.06 0.26 0.08 4.62 6 900 1.33 1.00 4.67 26.33 5.23 0.12 3789 7 8.33 9.30 4.14 0.06 0.45 0.05 4.69 9 110 0 130 0 150 0 1.33 1.00 4.33 23.33 9.67 0.13 3599 8 8.43 9.50 4.13 0.06 0.58 0.04 4.82 12 1.67 1.00 4.00 15.67 9.27 0.12 3873 10 8.33 9.37 3.99 0.08 0.71 0.03 4.81 15 1.33 1.00 6.33 15.00 6.30 0.20 3242 10 8.37 9.47 3.93 0.18 0.80 0.02 4.93 16 61 Post-Gypsum Incorporation Treatment No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp Plus irrig + Shallow gyp Dept h (cm) NO3 NH4 BicarbK (mg/kg) Avail-S (mg/kg) BicarbP (mg/kg) Ox-Fe EC pH pH Ex Ca Ex Mg Ex Na Ex K E (mg/kg) Org C (%) (mg/kg) (mg/kg) (mS/m) (H2O) (cmol/kg) (cmol/kg) (cmol/kg) (cmol/kg) ( 77.17 444.7 0.19 911 49 (CaCl2 ) 7.57 5 1.00 1.00 85.67 7.95 4.80 0.19 0.12 0.15 5 60 1.67 1.00 19.00 51.17 929.2 0.20 945 82 7.63 7.98 5.61 0.19 0.18 0.10 6 140 4.50 1.00 25.33 39.17 1007.5 0.23 887 93 7.75 8.20 5.99 0.23 0.64 0.09 6 5 1.33 1.00 53.83 66.67 244.5 0.18 1020 28 7.55 8.03 4.54 0.18 0.12 0.16 4 60 1.50 1.00 8.17 47.17 411.8 0.14 1061 43 7.72 8.13 4.63 0.14 0.20 0.10 5 140 4.17 1.00 14.33 38.00 459.3 0.14 1111 51 7.85 8.28 5.03 0.14 0.44 0.09 5 5 1.00 1.00 172.50 67.17 3042.7 0.28 760 138 7.25 7.38 10.49 0.28 0.08 0.14 1 60 1.17 1.00 6.67 64.00 199.6 0.11 1161 26 7.63 8.28 4.63 0.10 0.30 0.13 5 140 1.83 1.00 11.67 26.17 233.0 0.11 1173 32 7.87 8.38 4.43 0.11 0.82 0.06 5 5 1.17 1.00 79.17 71.33 2892.8 0.32 736 150 7.47 7.68 9.04 0.32 0.10 0.14 9 60 1.00 1.00 3.17 85.33 160.0 0.10 1134 24 7.55 8.25 4.83 0.09 0.12 0.15 5 140 1.83 1.00 7.58 28.17 474.1 0.10 1328 49 7.90 8.35 4.74 0.10 0.65 0.06 5 62 Appendix 4. Chemical properties of residue sand pre- and post- gypsum incorporation for the Kwinana site Pre-Gypsum Incorporation Treatment No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp Dept h (cm) NO3 NH4 BicarbP (mg/kg) BicarbK (mg/kg) AvailS (mg/kg ) Org C (%) Ox-Fe EC pH pH Ex Ca Ex Mg Ex Na Ex K ECEC (mg/kg ) (mg/kg ) 10 30 50 70 90 110 130 150 10 30 50 70 90 110 130 150 10 2.00 2.00 2.00 2.33 2.00 2.00 2.00 2.00 3.67 2.00 2.00 2.00 2.00 2.33 2.00 2.33 1.00 30 (mg/kg ) (mS/m ) (CaCl2 ) (H2O) (cmol/kg ) (cmol/kg ) (cmol/kg ) (cmol/kg ) (cmol/kg ) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 56.33 8.33 3.00 3.33 4.67 4.00 6.67 7.67 69.33 12.33 6.00 3.33 5.33 4.33 5.33 5.00 2.17 42.33 34.33 21.67 18.67 17.67 15.00 15.00 15.00 87.67 56.67 37.67 24.33 25.67 20.00 17.67 15.00 32.67 826 207 51 54 107 25 106 69 930 69 52 42 121 44 84 148 8 0.41 0.14 0.09 0.10 0.14 0.11 0.16 0.10 0.63 0.20 0.15 0.11 0.11 0.13 0.10 0.10 0.23 2007 2132 2642 3370 3453 3456 3519 2925 1784 2662 2787 3259 3308 3603 3413 2871 4004 79 37 12 15 14 14 23 25 87 22 15 14 17 16 19 26 41 7.80 7.87 7.97 8.03 8.30 8.27 8.27 8.23 7.63 8.07 8.00 8.07 8.23 8.23 8.27 8.20 8.07 8.27 8.60 8.90 9.00 9.23 9.40 9.20 9.40 8.03 8.90 8.97 8.97 9.20 9.30 9.27 9.27 9.82 7.92 6.68 5.89 6.09 5.35 4.96 5.29 5.09 8.44 6.91 7.56 6.20 5.81 5.49 5.62 5.05 2.79 0.11 0.08 0.11 0.10 0.12 0.09 0.08 0.09 0.20 0.17 0.17 0.11 0.09 0.09 0.08 0.08 0.09 0.17 0.14 0.20 0.35 0.69 1.02 1.39 1.54 0.22 0.71 0.44 0.84 0.86 1.06 1.19 1.66 3.37 0.08 0.08 0.05 0.03 0.03 0.01 0.02 0.02 0.14 0.11 0.08 0.03 0.04 0.03 0.03 0.02 0.10 8.29 6.98 6.24 6.58 6.19 6.09 6.78 6.74 9.00 7.90 8.25 7.18 6.80 6.67 6.92 6.82 6.35 2 2 3 5 11 17 20 23 3 8 5 11 12 15 17 24 51 1.00 1.00 2.50 15.50 8 0.21 3933 68 8.13 2.43 0.06 4.70 0.04 7.22 64 50 1.00 1.00 2.17 15.00 14 0.20 4440 94 8.18 2.06 0.06 6.06 0.04 8.22 74 70 1.00 1.00 3.00 15.17 19 0.19 4069 99 8.23 2.56 0.08 6.25 0.03 8.92 70 90 1.00 1.00 2.67 15.00 22 0.19 4236 102 8.18 2.17 0.06 6.30 0.03 8.56 73 110 1.00 1.00 3.33 15.00 25 0.17 4098 105 8.30 2.38 0.07 6.39 0.03 8.88 72 130 1.00 1.00 3.17 15.00 24 0.16 4002 103 8.23 2.27 0.06 6.18 0.03 8.54 72 150 1.00 1.00 2.50 15.00 24 0.19 3917 106 8.28 10.0 2 10.1 2 10.1 2 10.1 0 10.1 0 10.1 0 10.1 5 2.28 0.08 6.01 0.03 8.41 71 63 ES P (%) Plus gyp Plus gyp Plus gyp Plus gyp Plus gyp Plus gyp Plus gyp Plus gyp irrig + Shallow 10 1.00 1.00 2.17 32.67 8 0.23 4004 41 8.07 9.82 2.79 0.09 3.37 0.10 6.35 51 irrig + Shallow 30 1.00 1.00 2.50 15.50 8 0.21 3933 68 8.13 2.43 0.06 4.70 0.04 7.22 64 irrig + Shallow 50 1.00 1.00 2.17 15.00 14 0.20 4440 94 8.18 2.06 0.06 6.06 0.04 8.22 74 irrig + Shallow 70 1.00 1.00 3.00 15.17 19 0.19 4069 99 8.23 2.56 0.08 6.25 0.03 8.92 70 irrig + Shallow 90 1.00 1.00 2.67 15.00 22 0.19 4236 102 8.18 2.17 0.06 6.30 0.03 8.56 73 irrig + Shallow 110 1.00 1.00 3.33 15.00 25 0.17 4098 105 8.30 2.38 0.07 6.39 0.03 8.88 72 irrig + Shallow 130 1.00 1.00 3.17 15.00 24 0.16 4002 103 8.23 2.27 0.06 6.18 0.03 8.54 72 irrig + Shallow 150 1.00 1.00 2.50 15.00 24 0.19 3917 106 8.28 10.0 2 10.1 2 10.1 2 10.1 0 10.1 0 10.1 0 10.1 5 2.28 0.08 6.01 0.03 8.41 71 Total N (%) Total P (mg/k g) 0.02 8 0.02 3 0.02 8 0.02 3 0.02 0 0.02 2 0.02 8 0.02 7 0.03 0 167 Post-Gypsum Incorporation Treatment No irrig + Deep gyp No irrig + Deep gyp No irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp Plus irrig + Deep gyp No irrig + Shallow gyp No irrig + Shallow gyp No irrig + Shallow gyp Dept h (cm) NO3 NH4 BicarbK (mg/kg ) AvailS (mg/k g) Org C (%) Ox-Fe EC pH pH Ex Ca Ex Mg Ex Na Ex K ECEC (mg/k g) Bicarb -P (mg/kg ) (mg/k g) (mS/ m) (CaCl 2) (H2 O) (cmol/k g) (cmol/k g) (cmol/k g) (cmol/k g) (cmol/k g) ES P (% ) (mg/k g) 5 2.33 1.17 69.92 72.50 726 2241 77 7.83 0.21 0.44 0.14 7.74 6 7.25 1.00 9.83 23.42 1490 2417 107 8.03 8.20 0.19 0.94 0.05 9.39 12 140 1.17 1.00 13.42 18.08 593 2354 85 8.22 6.20 0.16 1.76 0.04 8.17 22 5 1.83 1.00 60.67 82.83 2594 2103 166 7.57 10.65 0.18 0.24 0.13 11.21 2 60 1.00 13.17 32.17 1821 1875 142 7.77 9.28 0.20 0.45 0.06 10.00 5 140 10.1 7 1.33 1.00 15.00 33.33 1571 2183 145 8.02 8.44 0.16 1.09 0.07 9.76 11 5 2.00 1.67 84.67 89.33 2965 2965 163 7.75 9.90 0.24 0.61 0.18 10.94 6 60 5.33 1.00 4.83 33.33 357 2965 50 8.10 3.99 0.14 2.35 0.08 6.56 36 140 1.17 1.00 15.50 19.17 594 2975 103 8.32 8.2 1 8.4 0 8.7 3 7.9 2 8.0 5 8.2 3 7.9 5 8.9 5 9.0 2 6.95 60 0.2 2 0.1 4 0.1 0 0.2 7 0.1 6 0.1 1 0.3 7 0.1 0 0.1 1 5.58 0.14 3.53 0.04 9.31 40 64 60 51 191 70 54 198 40 48 Plus irrig Shallow gyp Plus irrig Shallow gyp Plus irrig Shallow gyp + 5 M M M M M M M M M M M M M M M M M M + 60 M M M M M M M M M M M M M M M M M M + 140 M M M M M M M M M M M M M M M M M M 65 Appendix 5. Effect of time (pre- and post- (0, 6 and 12 months) after gypsum incorporation, on fertilizer and gypsum transport, and selected chemical properties. Values presented are for pre- and post- shallow gypsum incorporation, and minus irrigation. For each set of 4 graphs, (a) and (b) refer to data for the Kwinana trial, and (c) and (d) refer to data for the Pinjarra trial. Exchangeable Na (cmol/kg) Exchangeable Ca (cmol/kg) 0 (a) 20 40 0 60 (b) 0 4 6 0 40 80 Depth (cm) 40 Depth (cm) 2 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 80 120 160 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 Exchangeable Na (cmol/kg) Exchangeable Ca (cmol/kg) 0 20 40 0 60 (d) (c) 0 2 4 6 0 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 40 Depth (cm) Depth (cm) 40 80 120 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 80 120 160 160 66 2M KCl NO3 (mg/kg) 2M KCl NH4 (mg/kg) 0 (a) 0.4 0.8 1.2 1.6 0 2 (b) 0 Depth (cm) Depth (cm) 80 120 6 8 0 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 160 2M KCl NO3 (mg/kg) 2M KCl NH4 (mg/kg) 0 0.4 0.8 1.2 1.6 0 2 (d) (c) 0 2 4 6 8 0 40 Depth (cm) 40 Depth (cm) 4 40 40 80 120 2 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 160 67 1M KCl SO4 (mg/kg) Organic Carbon (%) 0 (a) 0.2 0.4 0.6 0 0.8 (b) 0 Depth (cm) Depth (cm) 80 120 6000 0 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 160 1M KCl SO4 (mg/kg) Organic Carbon (%) 0 0.2 0.4 0.6 0 0.8 (d) (c) 0 2000 4000 6000 0 40 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum Depth (cm) 40 Depth (cm) 4000 40 40 80 2000 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 120 160 160 68 Oxalate Al (mg/kg) Oxalate Fe (mg/kg) 0 (a) 2000 4000 6000 0 8000 10000 (b) 0 Depth (cm) Depth (cm) 2000 3000 4000 0 20 40 80 40 60 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 80 160 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 100 Oxalate Al (mg/kg) Oxalate Fe (mg/kg) 0 2000 4000 6000 0 8000 10000 (d) (c) 0 1000 2000 3000 0 20 Depth (cm) 40 Depth (cm) 1000 80 40 60 120 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 80 160 69 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 4000 Bicarbonate K (mg/kg) Bicarbonate P (mg/kg) 0 (a) 40 80 120 160 0 200 (b) 0 Depth (cm) Depth (cm) 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 120 0 80 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 120 160 160 Bicarbonate K (mg/kg) Bicarbonate P (mg/kg) 0 40 80 120 160 0 200 (d) (c) 0 40 80 120 0 40 Depth (cm) 40 Depth (cm) 80 40 40 80 120 40 80 120 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum 160 160 70 Pre-gypsum Post-gypsum 6mo Post-gypsum 12mo Post-gypsum K (mg/kg) 0 (a) 20 40 60 80 100 80 100 0 Depth (cm) 20 40 Available Soluble 60 80 K (mg/kg) 0 (b) 20 40 0 Depth (cm) 20 40 Available Soluble 60 80 71 60 NH4-N (mg/kg) 0 (a) 0.2 0.4 0.6 0.8 1 0.8 1 0 Depth (cm) 20 40 Available Soluble 60 80 NH4-N (mg/kg) 0 (b) 0.2 0.4 0.6 0 Depth (cm) 20 40 60 Available Soluble 80 100 72 NO3-N (mg/kg) 0 (a) 0.5 1 1.5 2 0 20 Depth (cm) 2.5 Available Soluble 40 60 80 NO3-N (mg/kg) 0 (b) 0.5 1 1.5 2 2.5 0 Depth (cm) 20 40 Available Soluble 60 80 100 73 P (mg/kg) 0 (a) 40 80 120 160 200 160 200 0 Depth (cm) 20 40 Available Soluble 60 80 P (mg/kg) 0 (b) 40 80 120 0 Depth (cm) 20 40 Available Soluble 60 80 74 Appendix 6a. Chemical Characteristics of Natural Topsoil, and Residue Sand Before (unamended) and After (1% gypsum amended) Gypsum Addition Topsoil Water-Soluble Fraction (Saturated paste analysis) Na (mg/L) 34.04 Mg (mg/L) 6.52 Al (mg/L) 50.15 PO4-P (mg/L) 0.47 SO4-S (mg/L) 8.65 Cl (mg/L) 58.10 K (mg/L) 4.96 Ca (mg/L) 18.45 Fe (mg/L) 20.45 NH4-N (mg/L) 4.06 NO3-N (mg/L) <0.01 EC (mS/m) 4.1 pH 6.12 θg (kg/kg) 0.32 HCO3 (mg/L) 373.20 CO3 (mg/L) <0.01 Unamended Gypsum-amended (1% gypsum) 2708 0.39 29.59 10.29 110 17.5 13.1 <0.01 8.0 0.2 0.6 11630 9.82 0.30 589 18380 2677 3.11 0.42 0.09 1804 7.9 40.6 111.9 0.3 2.6 0.7 13730 8.45 0.32 378 <0.01 Exchangeable or Available Fraction (after water-extraction) 2M KCl NO3-N (mg/kg) 5.3 3.0 2M KCl NH4-N (mg/kg) <0.01 1.0 Bicarbonate P (mg/kg) 2.1 4.0 Bicarbonate K (mg/kg) 37 24 Available S (mg/kg) 4.67 24 Organic C (%) 1.21 0.10 Amorphous-Fe (mg/kg) 96 2350 Amorphous-Al (mg/kg) 33 871 Exchangeable Ca (cmol/kg) 3.35 3.63 Exchangeable Mg (cmol/kg) 0.48 0.08 Exchangeable Na (cmol/kg) 0.11 5.53 Exchangeable K (cmol/kg) 0.04 0.06 Exchangeable Al (cmol/kg) 0.01 0.02 Exchangeable Fe (cmol/kg) 1.94 10.71 Total N (%) 0.02 0.02 Total P (mg/kg) 28.39 27 ECEC (cmol/kg) 3.98 9.32 3.0 1.0 7.0 36 634 0.19 2662 1007 5.76 0.08 4.18 0.09 0.03 6.59 0.02 60 10.14 75 Appendix 6b. Chemical Characteristics of a 4-year old Rehabilitated Residue Sand Profile (Watersoluble and exchangeable parameters) Exchangeable and Available Ions 1:5 1M KCl (BRS:Water) SO4-S EC (cm) (mg/kg) (dS/m) 1:5 1M (BRS:Water) NH4Cl/BaCl2 Exch pH Ca Exch Na (cmol/k g) (cmol/kg) 0-5 5 - 20 20 - 40 40 - 60 60 - 80 80 100 100 120 120 140 140 160 160 180 180 200 200 220 220 240 240 260 260 280 280 300 86 201 327 841 388 0.19 0.22 0.36 0.76 0.48 8.35 8.60 8.45 8.20 8.35 8.18 6.30 5.97 7.67 5.95 0.22 0.17 0.17 0.26 0.30 142 0.27 8.70 4.31 0.60 42 0.21 9.45 2.46 2.03 40 0.23 9.40 2.74 2.32 27 0.31 9.10 2.36 3.28 42 0.35 8.70 2.91 3.90 33 0.36 8.85 3.19 3.91 32 0.37 8.85 2.63 3.70 30 0.40 8.95 2.41 4.12 33 0.49 8.95 2.72 4.43 39 0.48 9.00 2.71 4.46 51 0.46 9.00 3.25 4.44 Depth Water Soluble Ions Depth Sol Ca Sol Na Sol SO4-S Sol CO32- Sol HCO3- (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) Sol Al (mg/ L) 7.54 7.54 7.34 7.37 7.31 203 372 491 687 589 57 58 67 101 115 480 294 379 551 468 0 0 0 0 0 51 37 26 28 27 0.84 <0.01 <0.01 <0.01 <0.01 1.80 7.62 316 281 373 0 43 0.02 1.79 2.15 9.26 9.35 5 3 412 544 115 112 0 0 322 409 2.93 2.56 θg EC (cm) (g/g) (dS/m) 0-5 5 - 20 20 - 40 40 - 60 60 - 80 80 100 100 120 120 - 0.42 0.34 0.35 0.37 0.37 1.08 1.38 1.74 2.19 1.95 0.34 0.36 0.35 pH 76 140 140 160 160 180 180 200 200 220 220 240 240 260 260 280 280 300 0.35 2.77 9.94 3 714 54 0 627 5.77 0.38 3.26 9.99 2 897 77 399 0 5.96 0.36 3.45 10.02 2 958 69 401 0 6.38 0.36 3.48 10.05 1 966 75 298 0 6.48 0.36 3.74 10.08 1 1065 69 425 0 7.21 0.35 4.00 10.14 1 1163 80 473 0 5.92 0.35 4.34 10.14 1 1299 113 383 0 8.89 0.36 4.62 10.18 1 1398 136 375 0 10.20 - 77 Appendix 7. Summary of botanical monitoring undertaken from 2005 to 2007 at Kwinana and Pinjarra irrigation trials and associated ANOVA Site Treatment Block # Year Pinjarra Irrigated (deep gypsum) 1 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2 3 Average NonIrrigated (deep gypsum) 1 2 3 Average Kwinana Irrigated (deep gypsum) 1 2 3 Average NonIrrigated (deep gypsum) 1 2 3 Average Density /m2 Natives (Exotics) 1.8 (1.6) 1.3 (4.7) 1.6 (8.0) 4.1 (0.7) 2.8 (11.9) 1.7 (11.9) 2.7 (0.5) 3.0 (8.6) 2.1 (27.6) 2.9 (0.9) 2.4 (8.4) 1.8 (15.8) 1.8 (0.8) 1.4 (5.4) 2.3 (16.4) 2.4 (1.5) 2.2 (38.3) 1.0 (32.2) 4.8 (1.5) 6.6 (15.2) 1.5 (38.3) 3.0 (0.9) 3.4 (19.6) 1.6 (29.0) 3.1 (3.1) 1.6 (1.8) 1.4 (4.8) 1.4 (4.7) 0.8 (2.8) 0.7 (2.9) 1.5 (9.3) 1.1 (3.3) 1.0 (17.9) 2.0 (5.7) 1.2 (2.5) 1.0 (8.5) 0.8 (4.8) 1.0 (4.0) 0.5 (21.2) 2.7 (6.4) 2.6 (2.2) 1.5 (23.0) 2.9 (5.3) 1.6 (4.4) 1.5 (24.0) 2.1 (5.2) 1.7 (3.5) 1.2 (22.7) 78 Cover Natives (Exotics) 2.2 (4.5) 83.5 (4.3) 93.9 (21.2) 1.7 (2.5) 112.9 (9.8) 146.0 (8.7) 2.3 (4.0) 76.9 (13.6) 93.1 (42.0) 2.1 (3.7) 91.1 (9.2) 111.0 (24.0) 2.4 (1.9) 44.1 (1.9) 76.2 (21.6) 1.7 (4.1) 42.7 (17.8) 54.2 (108.7) 3.1 (5.2) 53.0 (16.7) 81.0 (89.6) 2.4 (3.7) 46.6 (12.1) 70.5 (73.3) 2.6 (12.0) 37.1 (33.2) 56.9 (41.9) 1.7 (22.1) 29.9 (43.6) 39.4 (57.1) 0.7 (42.7) 30.6 (16.0) 49.3 (7.8) 1.7 (25.6) 32.5 (30.9) 48.5 (35.6) 1.1 (13.9) 20.8 (11.0) 47.0 (35.8) 1.5 (23.3) 20.2 (15.9) 47.6 (37.6) 0.8 (23.0) 9.7 (3.8) 40.0 (11.7) 1.1 (20.1) 16.9 (10.2) 44.9 (28.3) % Species Richness Natives (Exotics) 27 (4.5) 26 (5.5) 22.5 (6) 32.5 (10) 30 (9.5) 22 (7.5) 27 (7) 28 (8.5) 20 (7.5) 28.8 (7.2) 28 (7.8) 21.5 (7) 22 (5.5) 18.5 (7) 18.5 (7) 31.5 (8.5) 27.5 (10) 19.5 (5.5) 35.5 (8.5) 34.5 (8) 25.5 (8) 29.7 (7.5) 26.8 (6) 21.2 (6.8) 28.5 (7) 24.5 (5) 21.5 (8) 27.5 (9) 13.5 (6.5) 15.5 (6.5) 24.5 (9) 18 (6) 19 (7.5) 26.8 (8.3) 18.7 (5.8) 18.7 (7.3) 17.5 (9.5) 11.5 (5) 12 (6) 32 (9) 23.5 (7.5) 22 (8.5) 30.5 (7) 19.5 (4.5) 19.5 (10) 26.7 (8.5) 18.2 (5.7) 17.8 (8.2) Summary of ANOVA for cover, density and species richness across variables of block, rep, irrigation prescription, site, species and age of rehab. Significance levels **p<0.001, *p<0.05. Independent Variable Block (1, 2 &3) Irrigation (irrigated & non-irrigated) Rep (1 & 2) Site (KW & PJ) Species (Natives & Exotics) Year (2005, 2006, 2007) Cover Density * * Species Richness * * ** ** * ** ** * ** ** 79 Appendix 8. Summary of botanical monitoring undertaken from 2005 to 2007 at Kwinana and Pinjarra gypsum trials and associated ANOVA Site Treatment Block # Year Pinjarra Surface Gypsum (not irrigated) 1 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2005 2006 2007 2 3 Average Deep Gypsum (not irrigated) 1 2 3 Average Kwinana Surface Gypsum (not irrigated) 1 2 3 Average Deep Gypsum (not irrigated) 1 2 3 Average Density /m2 Natives (Exotics) 1.9 (1.0) 4.0 (8.8) 1.9 (36.4) 2.0 (2.6) 2.0 (28.8) 0.9 (33.8) 3.2 (5.4) 5.1 (45.6) 1.1 (47.1) 2.4 (3.0) 3.9 (27.7) 1.3 (39.1) 1.8 (0.8) 1.4 (5.3) 2.2 (16.4) 2.4 (1.5) 2.3 (38.2) 1.0 (32.2) 4.8 (1.5) 6.7 (15.2) 1.5 (38.3) 3.0 (1.3) 3.5 (19.6) 1.6 (29.0) 7.6 (0.2) 4.4 (9.6) 2.1 (11.7) 5.0 (0.2) 7.3 (8.2) 3.2 (17.5) 4.7 (0.5) 2.6 (11.4) 1.9 (8.4) 5.8 (0.3) 4.8 (9.7) 2.4 (12.5) 6.4 (0.2) 4.2 (4.8) 2.1 (18.9) 2.2 (0.1) 1.4 (6.2) 1.2 (4.1) 1.8 (0.7) 1.8 (17.1) 1.0 (10.7) 3.5 (0.3) 2.5 (9.4) 1.4 (11.2) 80 Cover Natives (Exotics) 1.6 (3.3) 32.3 (4.0) 44.3 (24.1) 1.7 (9.3) 29.4 (32.0) 43.3 (100.3) 1.8 (13.8) 16.8 (31.5) 27.3 (94.9) 1.7 (8.8) 26.2 (22.5) 38.3 (73.1) 2.5 (1.9) 44.1 (1.9) 76.2 (21.6) 1.7 (4.1) 42.7 (17.8) 54.2 (108.7) 3.2 (5.2) 53.0 (16.7) 81.0 (89.6) 2.5 (3.7) 46.6 (12.1) 70.5 (73.3) 5.0 (0.9) 37.5 (2.7) 41.0 (6.2) 3.7 (2.4) 30.4 (5.4) 29.7 (19.9) 3.7 (3.7) 37.4 (3.6) 34.4 (2.6) 4.1 (2.3) 35.1 (3.9) 35.0 (9.6) 3.5 (2.5) 23.4 (2.6) 41.4 (4.9) 2.3 (1.6) 19.4 (1.7) 35.3 (0.6) 1.6 (3.0) 27.4 (18.4) 23.8 (3.6) 2.5 (2.4) 23.4 (7.6) 33.5 (3.0) % Species Richness Natives (Exotics) 23.0 (8.0) 20.0 (9.5) 18.5 (10.5) 26.0 (12.5) 26.0 (9.5) 17.5 (7.5) 32.0 (16.5) 29.5 (12.5) 19.0 (7.5) 27.0 (12.3) 25.2 (10.5) 18.3 (8.5) 22.0 (5.5) 19.0 (6.5) 18.5 (7.0) 31.0 (9.0) 27.5 (10.0) 18.5 (6.5) 35.5 (8.5) 35.0 (7.5) 25.0 (8.5) 29.5 (7.7) 27.2 (8.0) 20.7 (7.3) 40.0 (3.5) 34.5 (6.5) 21.0 (7.5) 42.0 (1.5) 27.0 (5.0) 19.5 (5.5) 39.0 (1.0) 29.5 (3.5) 19.5 (4.5) 40.3 (2.0) 30.3 (5.0) 20.0 (5.8) 37.0 (3.5) 30.0 (7.0) 24.0 (6.5) 30.5 (3.0) 28.0 (5.5) 22.5 (5.5) 32.0 (3.0) 22.0 (4.5) 15.0 (4.5) 33.2 (3.2) 26.7 (5.7) 20.5 (5.5) Summary of ANOVA for cover, density and species richness across variables of block, rep, irrigation prescription, site, species and age of rehab. Significance levels **p<0.001, *p<0.05. Independent Variable Block (1, 2 &3) Gypsum Depth (surface & deep) Rep (1 upper slope, 2 lower slope) Site (KW & PJ) Species (Natives & Exotics) Year (2005, 2006, 2007) Cover Density ** * ** ** ** ** Species Richness * 81 ** **