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Can the application of rare earth elements improve yield and decrease the uptake of cadmium in ryegrass-dominated pastures?

Introduction

The rare earth elements (REEs) are a chemically similar group of 17 elements, including 15 elements with an atomic number from 57 (lanthanum; La) to 71 (lutetium; Lu) as well as scandium (Sc, 21) and yttrium (Y, 39). All the elements (except promethium; Pm) exist naturally in soil parent materials and total concentrations in soil vary from 16 to 219 mg [kg.sup.-1] (Hu et al. 2006). Rare earth elements are usually found as flurocarbonates, phosphates, silicates and oxides. Hence, commercially available rock phosphates contain REEs (Otero et al. 2005), which depending on their composition and use will influence soil REE concentrations (Tyler 2004).

Until recently, little attention had been paid to REEs as they were thought to be neither essential for life nor toxic. However, several researchers have purported to find significant increases in the yield of several crops. There have been several mechanisms given as causes such as: (i) increasing nutrient (N, phosphorus [P] and potassium [K] uptake, Liu et al. 1997); (ii) stimulating enzymes involved in N processes within the plant or in soil microbes (Liu et al. 1997; Zhu et al. 2002); (iii) increasing chlorophyll production (Guo 1993); and (iv) improving plant resilience to cold tolerance or drought (Guo et al. 1988). In addition, Wang et al. (2006) summarised several studies linking the application of REEs to decreased heavy metal uptake. However, there have also been many studies that may have been compromised by inadequate design or interpretation. For instance, Liu et al. (2006) reported yield increases of 10-24% for vegetable crops, but used control plots that were located in a different province to the treatment.

Studies that have reported better crop yields when applying REEs have a single commonality of low application rates, generally <10 kg [ha.sup.-1], and more commonly <1 2 kg [ha.sup.-1]. In contrast, studies such as those by Xu and Wang (2007) and Xie et al. (2002) have both demonstrated that rates >10 kg [ha.sup.-1] of REE application decreased yield in rice and maize. Consequently, there has been concern that long-term application of some REEs may harm soil and aquatic ecosystems (Boger et al. 1997; Wang et al. 2001; Brioschi et al. 2013), or bioaccumulate along the food chain (Liang et al. 2005). However, the lethal dose for 50% of the population ([LD.sub.50]) for La is similar to table salt (Wald 1990). Rambeck and Wehr (2005) point out that these results are likely to translate to other REEs, since similar chemical and biochemical behaviour span all REEs. Hence, while toxicity should be confirmed for each REE, their application at low rates to crops is unlikely to result in a toxicity issue.

In New Zealand, agriculture is dominated by ryegrass-white clover pastures, grazed by cattle, red deer and sheep. Farmers seek methods to produce pasture more efficiently, while also being conscious of potential environmental constraints such as the enrichment of topsoils with Cd arising from the application of P-fertilisers (Cadmium Working Group 2011; McDowell et al. 2013). We therefore hypothesised that the addition of REEs to soil at low rates (<2 kg [ha.sup.-1]) may benefit the yield of ryegrass-white clover pasture, while decreasing Cd uptake in foliage. To test this hypothesis we conducted a soil survey to determine background REE concentrations, and a series of glasshouse studies to determine environmental and soil conditions that affect ryegrass yield and Cd uptake following REE application, and can be used to explain responses tested in the field.

Materials and methods

Experimental studies were conducted in four stages: (i) a survey of New Zealand soils and fertilisers was conducted to determine the distribution and concentration of REEs in a range of New Zealand soils, and therefore the rate necessary to enrich soil REE concentrations above a natural background concentration; (ii) screening of a range of REEs, applied at a low rate, for their efficacy in improving ryegrass yield and decreasing Cd uptake in pot trials in a glasshouse; (Hi) further testing of REEs for yield and Cd uptake in the glasshouse under different soils, soil moistures and application rates and finally; (tv) testing of the best performing REE(s) from the glasshouse studies on existing ryegrass-white clover pastures in the field.

Soil and fertiliser survey

Ninety-nine soil samples were obtained from a previous trial (McDowell et al. 2013). Soils were classified by land use (dairy or sheep and beef) and their parent material (peat, sedimentary or volcanic). Rocks used in the manufacture of superphosphate were also obtained from Ballance Agri-Nutrients, Tauranga, New Zealand. Both soils and P-fertilisers were digested in concentrated nitric acid according to the method of Zhang and Shan (1997) and Cd and REEs (Ce, Dy [Dysprosium], Er [Erbium], Eu [Europium], Gd [Gadolinium], Ho [Holmium], La, Lu, Nd [Neodymium], Pr [Praseodymium], Sm [Samarium], Tb [Terbium], Th [Thorium], Tm [Thylium] and Yb [Ytterbium]) measured with an Inductively Coupled Plasma Optimal Emission Spectrophotometer (ICP-OES) with a Cetac U5000AT ultra sonic nebulizer.

Glasshouse screening of REEs

The soil chosen for the pot trial was a Warepa silt loam soil classified under the New Zealand soil classification system as a Pallie soil (USDA Classification: Udic Haplustept). Soil was obtained by scraping off the first 5 cm of topsoil (to minimise the influence of past fertiliser applications) from a permanent grassland and sampling the 5-10 cm layer. Intact soil cores were taken of this depth and bulk density determined using the method of Drewry et al. (2000). Extracted soil was air-dried for 4 weeks, crushed to <4 mm and thoroughly mixed. A subsample was crushed to <2 mm for analysis of anion exchange capacity (ASC), cation exchange capacity (CEC), Olsen P, pH, quick test K, and total C and N using the methods outlined in Blakemore et al. (1987). Mean chemical and physical characteristics of soils used in this paper are given in Table 1.

Approximately 3 kg of air-dried soil was then put into each pot and adjusted to 40% of available soil moisture (ASM; Grewal et al. 1990) determined as the difference between field capacity and wilting point: field capacity was 36% v/v and wilting point 13% v/v. Treatments were arranged in a randomised block design with a buffer-pot included between blocks and the outside of the trial.

After 2 weeks, 50 ryegrass seeds were sown per pot, allowed to germinate and culled to an average of 30 plants per pot to give both the same potential for foliage per pot (without treatment effects). Thirty days later foliage was cut 5 cm above the soil surface (to leave a residual dry matter (DM) equivalent to 1300 kg [ha.sup.-1]) and harvested. A temperature controlled greenhouse was used to grow the plants with temperature maintained at 22[degrees]C during the day and 10[degrees]C overnight. The pots were watered with an automatic overhead irrigation system that delivered ~2.5 mm twice per day. This was sufficient to keep the soil at ~30-40% ASM. During this establishment period, artificial lighting was used to extend the normal daylight period to 12 h.

An additional harvest occurred another three weeks later, after which it was assumed that the effect of a nutrient flush associated with rewetting dry soil was minimised (e.g. Fierer and Schimel 2002) and treatments were imposed.

Treatments with and without N (25 kg [ha.sup.-1]) were applied to the soil and foliage were in the form of REE (La, Ce, Y, Ho, Tb, Yb, and La and Ce combined) chlorides applied at 0.5 and 2.0 kg [ha.sup.-1], except for the La and Ce mixture which was applied at 0.5 kg La [ha.sup.-1] plus 0.5 kg Ce [ha.sup.-1]. These REEs were chosen due to their lower cost and easier availability compared with other REEs. There were eight replicates per treatment. Each REE (and N) treatment was applied as a spray (50 mL per pot): cited by Guo (1993) as the most common application method for crops such as barley, cotton, maize, rapeseed, rice, ryegrass, and sugar beet. Seven harvests were taken from the trial on a monthly basis. The plants were trimmed with hand shears to ~30-40 mm height and the foliage dried at 65[degrees]C for 48 h and weighed. A single bulk sample for each pot was made across harvests by combining all DM for a specific pot. The bulk samples were ground to <1 mm and analysed for La, Ce, Y, Ho, Tb, Yb and Cd concentration by ICP-OES following a nitric acid microwave digest (Zhang and Shan 1997). A sub-set of 10 foliage samples, across the range of concentrations measured, were also digested in a nitric acid-hydrogen peroxide mixture and measured by ICP-OES (Spalla et al. 2009). Concentrations were not statistically different to concentrations measured after a nitric acid digest. Hence, a decision was made to digest samples using the quicker and cheaper method of Zhang and Shan (1997).

Additional glasshouse testing

Following glasshouse screening, La was chosen for additional testing in three different soils and moisture regimes. The soils were a Horotiu silt loam (USDA Classification: Typic Udivitrand), a Lismore stony silt loam (considered analogous to the Warepa soil, which was unavailable; USDA Classification: Udic Haplustept) and a Conroy fine sandy loam (USDA Classification: Aridic Haplustalf), representative of the Allophanic, Pallic, and Semiarid New Zealand Soil Orders, respectively. Samples of each soil were obtained and analysed in the same manner as the initial glasshouse screening. Mean chemical and physical characteristics of each soil are given in Table 1.

For each soil type, ~3 kg of air-dried soil was put into each pot and adjusted to 20, 40 or 70% ASM. Wilting point for the Horotiu, Lismore and Conroy soils was, 23, 18 and 19% v/v, respectively; while the corresponding field capacity values were 48, 38 and 34% v/v. Soils were maintained at these moistures by weighing a subsample of pots every few days and watering if necessary. A row of buffer-pots were arranged around the outside of the trial to minimise edge effects. Ryegrass was treated as per the initial screening experiment for 9 weeks. One month after initialisation the first harvest was taken. The La treatments were then sprayed onto each soil by moisture treatment at a rate of 0,0.5,1.0,5 or 10 kg La [ha.sup.-1], each with five replicates (i.e. 75 pots per soil). Foliage was harvested three times before another La application was made at the same rates and three more harvests made, giving a total of seven harvests and two REE applications. Treatments are referred to as the sum of La applied (e.g. the greatest rate was 20 kg La [ha.sup.-1]).

Following a preliminary analysis of the first three harvests, data suggested that there was a yield effect due to La application. Unfortunately, we could not determine if this also resulted in different chemical composition (e.g. less Cd in foliage) in a bulked sample due to the loss of the second harvest. Foliage from the control and 20 kg La [ha.sup.-1] treatments of the first harvest after the second application of La was dried, ground <1 mm, acid digested (Kalra et al. 1989) and analysed via ICP-OES for total N, P, K and Cd concentrations.

Field trial

A field trial sites was established on the AgResearch Invermay research farm (Warepa silt loam: USDA Classification; Udic Haplustept) near Dunedin, New Zealand. The site supported a mixed clover and ryegrass pasture grazed by sheep and received regular dressings of superphosphate (10 kg P [ha.sup.-1] [year.sup.-1]) and limestone (1 Mg [ha.sup.-1] every 3 4 years). The trial began in spring, 2011 and ran for 2 years.

The site was fenced to exclude stock and DM harvested and removed to a uniform height of 5 cm above the soil surface (~1300 kg [ha.sup.-1] residual cover). Forty eight plots (2 m x 1 m with a 1 m buffer area between) were established. A calibration cut was carried out initially to help standardise natural variation between plots.

The plots were arranged in a grid, with six replicates each of La applied at zero, 0.5 kg [ha.sup.-1], 0.5 kg La [ha.sup.-1] plus 0.5kg Ce [ha.sup.-1], or 2 kg La [ha.sup.-1], all with and without N applied at 25 kg [ha.sup.-1] (as urea). Treatments, designed to be consistent with the glasshouse trial, were applied in spring and late summer using analytical grade La[Cl.sub.3] x 7[H.sub.2]0, Ce[Cl.sub.3] x 7[H.sub.2]0, and urea dissolved into 1 L of deionised water then sprayed onto each plot ensuring even application to foliage and soil surface. Application took place 10-14 days after harvest dates to allow for sufficient fresh foliage to uptake the REEs and/or N.

Seven harvests were taken at approximately monthly intervals during the growing season (Sept.-May), using a rotary mower set at a height of 5 cm above the soil surface (to leave residual dry matter of ~1300 kg [ha.sup.-1]). Foliage was weighed and a 200-300 g representative sub-sample dried at 65[degrees]C for 48 h and re-weighed to estimate DM yield. In addition to a sample bulked across all harvests, individual samples for harvests taken two and seven weeks after the first REE application were also ground <1 mm, nitric acid microwave digested (Zhang and Shan 1997) and analysed via ICP-OES for total Cd.

Statistical analyses

All data was log-transformed before analysis if not normally distributed before being analysed by ANOVA and checking residuals for homoscedasticity.

For the soil survey, point-wise data for each REE were analysed by ANOVA, fitting terms for the factorial interaction of soil parent material and land use.

For the initial glasshouse screening, cumulative yield per pot after REE application DM and mean Cd concentrations were analysed by ANOVA, fitting terms for the factorial interaction of REE type, rate and N application. After the isolation of a N effect, treatments were compared using a Duncan's multiple range test.

For the additional glasshouse testing, mean DM yield for all harvests and Cd concentration in foliage for the harvest following the second La application were analysed by ANOVA fitting terms for the factorial interaction of soil type and soil moisture with La application. For simplicity, a comparison (i-test) of Cd concentrations was made at 0 and 20 (i.e. 2 x 10 kg [ha.sup.-1]) application rates.

For the field trial an ANOVA was then used to compare cumulative yield between treatments and Cd concentrations in selected harvests after REE application, with comparisons made between treatments and years with a Duncan's multiple range test. A calibration cut was used as a covariate in the analysis of data to account for inherent differences in DM between the plots.

Results

Soil survey

Data for the mean concentrations of REEs and Cd in soils and fertilisers are given in Table 2. The concentrations of many REEs were greater in Volcanic compared with Sedimentary soils. A greater concentration of REEs in Peat soils compared with Sedimentary soils reflected the lower bulk density of the Peat soils. Dairy soils were also more enriched in certain REEs (Ce, Eu, La and Nd) compared with Sheep and Beef soils. This enrichment may have been caused by the greater application of P-fertilisers to dairy soils, since the same four REEs were also enriched relative to other elements in the P-fertilisers analysed. Zhang et al. (2006) estimated that the application of 320 kg [ha.sup.-1] [year.sup.-1] superphosphate manufactured in Zhinjin County, China, would supply between 38-189 g REE [ha.sup.-1] annually to plants.

The concentration of REEs in soil is also influenced by parent material decreasing from: granite > quaternary > basalt > sandstone (Hu et al. 2006). Loessial and calcareous soils tend to have lower total REE concentrations (137-174 mg [kg.sup.-1]) than those derived from igneous rock or sandstone (174-219 mg [kg.sup.-1]). Surveys have thus far shown the greatest enrichment of REEs in soils from China, which had a mean total REE concentration of 177 mg [kg.sup.-1], whereas studies of soils in other countries put mean concentrations at between 18 and 118 mg [kg.sup.-1] (Hu et al. 2006). The range of parent materials in our (New Zealand) survey resulted in a mean total concentration of REEs 67 mg [kg.sup.-1], greater than soils from Germany or the USA, but less than soils from Australia, Sweden, Japan or Malaysia. We therefore conclude that the mean REE concentration in New Zealand soils is no more enriched than those from many other countries, but localised enrichment due to soil order or land use may occur.

Glasshouse screening

The addition of N significantly (P< 0.001) increased overall DM yield by 32% (Table 3). Additional analysis of DM in REE treatments either with or without N additions showed that there were both increases and decreases in yield compared with the control. However, Ho decreased yield by >5% irrespective of N additions while a similar decrease occurred for Y addition in conjunction with N. Hence, both were discounted from further investigation. Interestingly, of the REEs that remained--La and Ce; both are included in commercial REE fertilisers available from China (e.g. Changle[TM] contains 25% Ce[0.sub.2] and 12% La[0.sub.3]; Xiong et al. 2000). After considering the availability and price of the REEs that remained (Arafura Resources 2013), La and Ce were selected as readily available and of low enough cost to warrant further testing.

Application of N had no effect on Cd concentrations (Table 3). The addition of La averaged across the 2.0 kg [ha.sup.-1] application rates (irrespective of N addition) decreased Cd foliage concentration by -18% compared with the control (Table 3). The effects of adding other REEs were not significant. For its potential yield and effect on decreasing Cd uptake, La was the focus of additional glasshouse and field testing.

Additional glasshouse testing

Overall DM yield was affected by the rate of La applied in the Conroy and Lismore soils (Fig. 1), but not in the Horotiu soil perhaps because of a greater REE concentration in the Volcanicderived Horotiu soil compared with the Sedimentary-derived Conroy and Lismore soils. When broken into individual harvests, overall yield was largely accounted for by increases for the two harvests after La was applied to the Conroy soil and for the first harvest after application for the Lismore soil (Fig. 2).

Data from the first harvest after the second application of La showed that Cd concentrations in foliage paralleled soil Cd concentrations, greatest in the Horotiu soil and least in the Conroy soil (Tables 1 and 4). On average, concentrations of Cd in foliage decreased in the 20 kg La [ha.sup.-1] treatment compared with the control by 60, 40 and 30% in the Conroy, Lismore and Horotiu soils, respectively.

Field trial

Summarising the effects of treatments in the first year, the addition of N increased DM yield over the control by 9%, 17% when N was added with 0.5 kg La [ha.sup.-1], and 4% when only 0.5 kg La [ha.sup.-1] was added (Table 5). The addition of 2 kg La [ha.sup.-1] with N increased yield by -10%, but decreased yield without N added. No other treatments were significant. During the second year only treatments with N added improved yield over the control (Table 5). Notably, mean annual temperature during year one was close to the 30 year average, but much cooler in the second year (annual temperature 1.3[degrees]C below the 30 year average).

Foliage composition data for a sample of all harvests and both years showed that mean N, P and S concentrations were consistent across the treatments and sites, but K concentrations were slightly enriched for the 0.5 kg La [ha.sup.-1] and 0.5 kg La+ 0.05 kg Ce [ha.sup.-1] treatments (Table 6). The concentration of Cd determined in foliage taken in the first harvest two weeks after application showed more significant decreases relative to the control compared with harvests taken seven weeks after the first and second treatment application. However, there was no overall effect on Cd concentration, suggesting that any decrease in Cd enrichment of foliage was short lived.

Discussion

Effect on yield and Cd concentrations in foliage

Both glasshouse and field trials indicated mixed results with a modest increase in DM yield following the application of La, but only under specific conditions of low soil REE concentration and soil moisture. The DM responses to La were consistent with the little literature that exists on the impact of REE. For example, both the Conroy and Lismore soils contained lower concentrations of La and Ce than the Horotiu soil and hence were more likely to exhibit La response. The Conroy and Lismore soils also had less ASM (14% v/v and 20% v/v, respectively) than the Horotiu soil (25% v/v), and were therefore more likely to promote plant water stress--a condition Buckingham et al. (1999) attributed as a likely cause for summer yield improvements of 24% for ryegrass on a sandy soil in Victoria, Australia. Similarly, increases in K concentrations when treated with La or Ce were similar to those exhibited in rice (12 and 9% for P and K, respectively; Ning and Xiao 1989) and wheat (8% for P; Zhu et al. 1994). However, this is probably due to the stimulation of K uptake caused by the addition of REEs as chlorides rather than a REE effect (Bloom and Finazzo 1986). This is supported by the fact that all three soils had P and K concentrations considered greater than that required for optimal pasture growth (Edmeades et al. 2010).

Soil chemical properties may have also influenced Cd concentrations in foliage. For instance, mean concentrations in foliage paralleled the Cd concentrations and pH (which increases Cd uptake with increasing acidity) among the different soils. However, there are also reports indicating that REEs can decrease Cd concentrations when sprayed onto foliage, irrespective of soil type (Liu et al. 1997; Wang et al. 2006), although the mechanism causing the decrease in Cd concentration is unclear.

There are several reports showing an interaction between Cd uptake and N applications. For instance, Li et al. (2011) reported a 64% increase in Cd uptake for wheat when N was applied. However, both increases and decreases have been noted. Generally, a dilution effect is ascribed to plant growth quicker than the rate of Cd desorption from solid to liquid phase into soil solution (Landberg and Greger 2003; Wangstrand et al. 2007), whereas enrichment has been noted where Cd supply is good and conditions are favourable for growth.

Climatic conditions in the glasshouse studies were controlled. However, in the field, cool temperatures (annual temperature 1.3[degrees]C below the 30 year average) may have contributed to a lack of a REE effect in the second year. Similarly, periods of water stress which yielded improvements in ryegrass yield in Victoria, Australia (Buckingham et al. 1999) were rare for the months following treatment applications. Clearly, more work is required to establish any mechanism of action, but even in a soil where the effect of adding REEs is likely, yield and Cd uptake responses were modest and short-lived.

Management

The commonly available REEs are Ce and La chloride or nitrate salts. These materials are highly soluble but crystalline in nature. Application of the pure salts would require the use of spray application as the crystals are not suitable for broadcast or spin application to fields. In addition, consistent application across a field will be problematic due to the low application rates of 0.5 kg REE [ha.sup.-1]. The most convenient method for application of REEs is utilising their compatibility with a urea-N solution which can be spray applied or delivered via fertigation to ensure even coverage to the target crop or pasture.

Rare earth elements are expensive relative to other agronomically important nutrients such as N, P or S. The high relative cost is not due to the technology to extract the elements, but mostly due to the international trade and market conditions, which are dominated by China. Since at least 2009, China has had export restrictions on REE exports with exporters subject to quotas on supply (Hurst 2010). As a consequence, REE prices have been volatile over this period with the La oxide price exceeding $US60[kg.sup.-1] (Arafura Resources 2013). With prices consistently over $US10 [kg.sup.-1] for La oxide since 2009, a large yield response would need to occur to offset costs. The results showed that the widespread use of REEs such as La is uneconomic due to the narrow range environmental conditions and soils with low enough REE concentrations to possibly show a yield response. Environmentally, the inhibition of Cd uptake was also only short-term. Moreover, repeated applications of REEs may lead to their accumulation in the soil to concentrations that may become problematic, such as for the germination or growth of some crops (Thomas et al. 2014).

Conclusions

Soil survey data indicated that mean concentrations of many REEs were enriched in Volcanic compared with Sedimentary soils and for soils used for dairying compared with sheep and beef. Land use differences were attributed to factors such as inputs by REE-rich P-fertilisers. From a range of REEs, La and Ce showed some potential to increase DM yield of ryegrass. However, additional glasshouse testing only showed a yield improvement for two soils with low La and Ce concentration that received low rates of La and were maintained at 40% ASM or less. A mixed response was also evident in the field, with the addition of La only boosting yield at low rates (0.5 kg [ha.sup.-1]) and in one year when temperatures and soil moisture were near the 30 year average. Applying La caused a decrease in Cd concentrations in foliage for the first harvest after application, but did not result in a significant decrease over all harvests. Hence, we conclude that there was insufficient data to warrant the use of La (screened from a range of REEs) as a strategy to increase dry matter yield and decrease Cd concentrations in ryegrass-dominated pastures in New Zealand.

http://dx.doi.org/10.1071/SR15073

Acknowledgements

This work was supported by the Ballance Agri-Nutrients' Primary Growth Partnership with the Ministry for Primary Industries entitled 'Clearview'.

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R. W. McDowell (A,B,D), W. Catto (C), and T. Orchiston (A)

(A) AgResearch, Invermay Agricultural Centre, Private Bag 50034 Mosgiel, New Zealand.

(B) Faculty of Agriculture and Life Sciences, Lincoln University. Lincoln 7647, New Zealand.

(C) Ballance Agri-Nutrients, Private Bag 12503, Tauranga, New Zealand.

(D) Corresponding author. Email: richard.mcdowell@agresearch.co.nz

Table 1. Mean chemical and physical characteristics of soil
(New Zealand soil order in parentheses) used in the initial
screening, additional glasshouse testing and the field trial

Parameter              Initial       Horotiu      Additional   Conroy
                      scrcening/   (Allophanic)   glasshouse   (Semi-
                        Field                      testing     arid)
                        trial                      Lismore
                        Warepa                     (Pallie)
                       (Pallie)

ASC (%)                   24            84            26         7
CEC (me 100               14            20            15         8
  [g.sup.-1])
Bulk density               1.03          0.88          1.02       1.02
  (g [cm.sup.-3])
Olsen P                    7            28            10         25
  (mg [L.sup.-1])
pH                         5.9           5.1           5.7        7.1
Quick test K (A)           6             8             8          6
Total Cd                   0.25          0.70          0.07       0.05
  (mg [kg.sup.-1])
Total C                   37            57            31         14
  (g [kg.sup.-1])
Total N                    3.1           6.3           3.0        1.7
  (g [kg.sup.-1])

(A) Quick test unit = 20.8 x bulk density (g [cm.sup.-3])
x exchangeable K (me 100 [g.sup.-1]).

Table 2. Mean concentration (mg [kg.sup.-1]) of Cd and rare
earth elements in soils and fertilisers by land use and soil
parent material

The F-statistic is also given for the significance of
treatment comparisons by land use, soil parent material and
their interaction. Enrichment ratio is the quotient of
overall mean P-fertiliser and soil mean concentrations for
each REE. Shaded cells indicate those REEs most enriched,
and thereby indicative of, P-fertilisers

Soil parent material      Cd       Ce       Dy       Er

Peat                     1.43     9.3      2.2      4.2
Sedimentary              0.77     8.2      3.1      3.3
Volcanic                 0.99     26.2     4.9      6.6
Sedimentary              0.90     8.6      3.6      4.2
Volcanic                 1.01     18.6     4.2      4.6
Land use                0.455    0.036    0.691    0.294
Soil                    <0.001   <0.001   <0.001   <0.001
Interaction             0.427    0.027    0.175    <0.001
P-fertilisers             --      76.5     13.4     13.6
Overall soils mean        --      13.8     3.7      4.5
Enrichment ratio          --      5.6      3.6      3.0

Soil parent material      Eu       Gd       Ho       La

Peat                     13.3     0.9      0.2      4.8
Sedimentary              6.6      0.6      0.1      3.2
Volcanic                 4.2      2.4      0.4      23.2
Sedimentary              5.5      0.7      0.1      3.9
Volcanic                 2.6      1.5      0.3      16.2
Land use                <0.001   0.052    0.078    0.085
Soil                    <0.001   <0.001   <0.001   <0.001
Interaction             0.707    0.027    0.047    0.066
P-fertilisers           130.2     5.2      1.2      52.1
Overall soils mean       5.7      1.2      0.2      9.7
Enrichment ratio         22.8     4.5      5.2      5.4

Soil parent material      Lu       Nd       Pr       Sm

Peat                     0.1      36.9     1.1      1.1
Sedimentary              0.3      11.8     1.2      1.8
Volcanic                 0.4      29.8     4.8      3.9
Sedimentary              0.4      15.1     1.4      2.1
Volcanic                 0.4      13.8     3.8      3.4
Land use                0.024    0.002    0.298    0.745
Soil                    <0.001   <0.001   <0.001   <0.001
Interaction             0.694    0.001    0.137    0.196
P-fertilisers            0.8     445.4     6.9      5.7
Overall soils mean       0.4      19.1     2.4      2.5
Enrichment ratio         2.1      23.3     2.8      2.3

Soil parent material      Tb       Th      Tm       Yb

Peat                     0.2      0.1      0.2     0.5
Sedimentary              0.5      0.5      0.4     0.4
Volcanic                 0.7      0.2      0.6     1.2
Sedimentary              0.5      0.1      0.5     0.4
Volcanic                 0.6      0.8      0.8     0.8
Land use                0.158    0.496    0.173   0.075
Soil                    <0.001   0.110    0.008   <0.001
Interaction             0.365    <0.001   0.677   0.034
P-fertilisers            0.9      3.4      0.5     4.0
Overall soils mean       0.5      0.3      0.5     0.6
Enrichment ratio         1.6      10.4     0.9     6.2

Table 3. Mean dry matter (DM) total yield (mg [pot.sup.-1])
and Cd concentration (mg [kg.sup.-1]) of foliage from the
initial glasshouse screening pot trial

Treatments for yield or Cd concentration are compared within
each N application rate using Duncan's multiple range test
at the P = 0.05 level of significance. Within each row,
means followed by the same letter are not significantly
different

Treatment                0kg N [ha.sup-1]      25 kg N [ha.sup.-1]

                         DM yield   Cd cone.   DM yield   Cd cone

Control                   3094a      0.175a     3874a      0.205a
0.5 kg [ha.sup.-1] Ce     3259b      0.179a     3706a      0.183a
2 kg [ha.sup.-1] Ce       3468c      0.164a     3812a      0.179a
0.5 kg [ha.sup.-1] Ho     2732b      0.199a     3802a      0.193a
2 kg [ha.sup.-1] Ho       2788b      0.196a     3847a      0.202a
0.5 kg [ha.sup.-1] La     3194a      0.149b     3777a      0.176a
2 kg [ha.sup.-1] La       3346c      0.143b     4153b      0.165b
0.5 kg [ha.sup.-1] Tb     3173a      0.166a     3877a      0.173a
2 kg [ha.sup.-1] Tb       3135a      0.174a     4043a      0.169a
0.5 kg [ha.sup.-1] Yb     3065a      0.199a     3985a      0.172a
2 kg [ha.sup.-1] Yb       3106a      0.164a     3987a      0.194a
0.5 kg [ha.sup.-1] Y      3102a      0.178a     3163c      0.181a
2 kg [ha.sup.-1] Y        3353c      0.163a     3670c      0.184a
0.5 kg ha 1 La + 0.5      3177a      0.145b     3938a      0.178a
  kg [ha.sup.-1] Ce

Table 4. Mean Cd concentration in foliage from the first
harvest after the second application of La in the additional
glasshouse trial

The F-statistic for the significance of treatment
comparisons is given for soil type, La application rate,
soil moisture and their interactions. An asterisk indicates
a significant contrast between each La by soil type by soil
moisture treatment and the control using a pairwise t-test

Soil type             La rate (kg      Soil            Cd
                      [ha.sup.-1])   moisture   (mg [kg.sup.-1])
                                     (% v/v)

Conroy (Semi-arid)          0           20           0.171
                           --           40           0.060
                                        70           0.048
                           20           20           0.040 *
                                        40           0.031 *
                                        70           0.042
Lismore (Pallie)            0           20           0.127
                                        40           0.289
                                        70           0.090
                           20           20           0.077 *
                                        40           0.152 *
                                        70           0.067
Horotiu (Volcanic)          0           20           0.338
                                        40           0.343
                                        70           0.284
                           20           20           0.302
                           --           40           0.253 *
                           --           70           0.223
Soil                                                <0.001
La rate                                              0.002
Moisture                                             0.023
Soil x La rate                                       0.923
Soil x moisture                                      0.028
La rate x moisture                                   0.501
Soil x La rate x                                     0.449
  moisture

Table 5. Mean dry matter yield (kg [ha.sup.-1]) for two
years in the field trial at Invermay

Mean yields for each year are compared between treatments
using Duncan's multiple range test at the P=0.05 level of
significance. Within each row, means followed by the same
letter are not significantly different

Treatment                                        Year 1   Year 2

Control                                          8090a    6000a
25 kg [ha.sup.-1] N                              8820b    6700b
0.5 kg [ha.sup.-1] La                            8500b    6350a
0.5 kg [ha.sup.-1] La+ 25 kg [ha.sup.-1] N       9450c    7150b
0.5 kg [ha.sup.-1] La + 0.5 kg [ha.sup.-1] Ce    7780a    5950a
0.5 kg [ha.sup.-1] La + 0.5 kg [ha.sup.-1]       9190b    6950b
  Ce + 25 kg N
2 kg [ha.sup.-1] La                              7660a    6100a
2 kg [ha.sup.-1] La + 25 kg Ce+ 25 kg N N        8930b    7100b

Table 6. Mean N, P, K, S and Cd concentration in a bulked
sample of foliage from all harvests taken from the field
trial, and the mean Cd concentration in foliage sampled from
the first harvest after the first REE application in year I
and the second REE application in year 2

Mean concentrations are compared between treatments using
Duncan's multiple range test at the P 0.05 level of
significance. Within each row, means followed by the same
letter are not significantly different

Treatment                       N                 P
                         (g [kg.sup.-1])   (g [kg.sup.-1])

Control                       29.2a             4.1a
25 kg [ha.sup.-1] N           29.9a             4.2a
0.5 kg [ha.sup.-1] La         29.2a             4.3a
0.5 kg [ha.sup.-1]            29.8a             4.2a
  La + 25 kg
  [ha.sup.-1] N
0.5 kg [ha.sup.-1]            28.7a             4.2a
  La + 0.5 kg
  [ha.sup.-1] Ce
0.5 kg [ha.sup.-1]            29.4a             4.2a
  La + 0.5 kg
  [ha.sup.-1]
  Ce + 25 kg N
2 kg [ha.sup.-1] La           28.3a             4.3a
2 kg [ha.sup.-1]              29.9a             4.2a
  La + 25 kg
  [ha.sup.-1] N

Treatment                       K                 S
                         (g [kg.sup.-1])   (g [kg.sup.-1])

Control                       16.1a             4.4a
25 kg [ha.sup.-1] N           15.5a             4.2a
0.5 kg [ha.sup.-1] La         17.6b             4.5a
0.5 kg [ha.sup.-1]            16.5a             4.3a
  La + 25 kg
  [ha.sup.-1] N
0.5 kg [ha.sup.-1]            16.9a             4.5a
  La + 0.5 kg
  [ha.sup.-1] Ce
0.5 kg [ha.sup.-1]            18.0b             4.3a
  La + 0.5 kg
  [ha.sup.-1]
  Ce + 25 kg N
2 kg [ha.sup.-1] La           17.0a             4.6a
2 kg [ha.sup.-1]              16.6a             4.3a
  La + 25 kg
  [ha.sup.-1] N

Treatment                       Cd           Concentration of
                         (mg [kg.sup.-1])   Cd (mg [kg.sup.-1])
                                               2 weeks after
                                              1st application

Control                       0.110a              0.190a
25 kg [ha.sup.-1] N           0.122a              0.186a
0.5 kg [ha.sup.-1] La         0.081a              0.110b
0.5 kg [ha.sup.-1]            0.104a              0.127b
  La + 25 kg
  [ha.sup.-1] N
0.5 kg [ha.sup.-1]            0.122a             0.137a,b
  La + 0.5 kg
  [ha.sup.-1] Ce
0.5 kg [ha.sup.-1]            0.093a              0.117b
  La + 0.5 kg
  [ha.sup.-1]
  Ce + 25 kg N
2 kg [ha.sup.-1] La           0.106a              0.135b
2 kg [ha.sup.-1]              0.109a              0.114b
  La + 25 kg
  [ha.sup.-1] N

Treatment                 Concentration of
                         Cd (mg [kg.sup.-1])
                            7 weeks after
                           1st application

Control                        0.185a
25 kg [ha.sup.-1] N            0.177a
0.5 kg [ha.sup.-1] La          0.155a
0.5 kg [ha.sup.-1]             0.175a
  La + 25 kg
  [ha.sup.-1] N
0.5 kg [ha.sup.-1]             0.155a
  La + 0.5 kg
  [ha.sup.-1] Ce
0.5 kg [ha.sup.-1]             0.169a
  La + 0.5 kg
  [ha.sup.-1]
  Ce + 25 kg N
2 kg [ha.sup.-1] La            0.171a
2 kg [ha.sup.-1]               0.148a
  La + 25 kg
  [ha.sup.-1] N
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Author:McDowell, R.W.; Catto, W.; Orchiston, T.
Publication:Soil Research
Article Type:Report
Date:Oct 1, 2015
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