Long-Term Effect of Phosphate Fertilization on Cadmium Uptake by Oat and its Accumulation in Soil
Received Date: Oct 03, 2017 / Accepted Date: Oct 09, 2017 / Published Date: Oct 14, 2017
Phosphate fertilizers contain varying amounts of cadmium (Cd) and other heavy metals as contaminants from phosphate rock (PR). Periodic applications of these fertilizers could result in measurable accumulations of Cd in soils and in harvested crops. A long term field study for fifteen cropping seasons (1992-2006) was conducted on an experimental plot located at the Norwegian University of Life Sciences (Ås, Norway) to evaluate the effect of application of cadmium enriched phosphate fertilizer on Cd uptake by Oat (Avena sativa) and its accumulation and availability in soil. Treatments consisted of three NPK fertilizer sources containing 1, 90, 381 mg Cd kg-1 P and applied at the rate of 0.03, 2.7, 11.43 g Cd ha-1yr-1, respectively. Surface soil samples (0-20 cm), collected after harvesting of oat in 1992, 1995, and 2006, and were analyzed for total and extractable Cd, pH, dissolve organic carbon (DOC) and PO4 3-. Plant samples collected in 1992, 1995, 1997, 2002 and 2006 were analyzed total Cd. Plant Cd generally decreased with increased soil pH throughout the experimental period except 1992. Increased input of Cd through fertilizers increased the Cd concentration in soil but the Cd concentration in oat grain remained unaffected. Ammonium nitrate (NH4NO3 -) extractable Cd in the soil increased with increasing rate of Cd through different sources but it decreased with increased pH throughout the experimental period with minor exceptions. Plant Cd did not show any significant correlation with extractable Cd in soil and hence the Cd input through fertilizers did not significantly affect the concentration of Cd in oat grain. Model (WHAM) prediction of Cd uptake by plants showed that crop yield, pH and DOC in combination explained about 57% of the variation in Cd uptake and DOC (r2=0.47, p<0.0001) was the most important factor. However, in individual years (e.g.2006) the combination of FA-Cd and yield did in fact explain 92% of the Cd-uptake.
Keywords: Cadmium; Cd uptake; Extractable Cd; NPK fertilizers; Oats; Plant Cd; Phosphate fertilizers; Soil pH; Soil solution; Modelling
Since the middle of the last century, commercial fertilizers have played a critical role in increasing food and fiber production around the world. However, these fertilizers may also contain some nonessential and harmful elements such as cadmium, lead and/or arsenic . There is a concern that continuous use of such fertilizers over a long period may cause an accumulation of trace elements to high levels, which ultimately increases the risk to environmental and human health . Cadmium (Cd), in addition to its natural presence in soils, can be introduced through anthropogenic activities, e.g. Fertilization, organic waste disposal and atmospheric deposition . Although P fertilizers represent the major anthropogenic input of phosphorus to agricultural soils, both inorganic P fertilizers and organic P sources (sewage, sludge and manure) contain Cd3 . In addition to direct inputs of Cd, phosphorus fertilizer can indirectly affect Cd accumulation in crops through its effects on soil chemistry, crop growth, and microbial interactions . Most of trace elements are persistent in soil because of their relative immobility in soils. However, Cd is more mobile and soluble than other trace elements contained in fertilizers . Cadmium is present in plant materials due to its uptake from soil . The availability of Cd in soil and its uptake by plant depend on several soil and plant factors. Cadmium enters human body from environment through ingestion via food (especially plant-based food) mechanism .
When we apply phosphorus fertilizer to our cropland, trace element, especially Cd, also enter soil as fertilizer contaminants [8,9]. The amount of Cd taken up by an individual plant depends on the amount of bioavailable Cd present in the soil  and the physiological and morphological characteristics of the plant . In a short-term growth chamber study, increase in Cd concentration in durum wheat by P fertilization was caused by increased uptake and translocation by decreasing Zn accumulation by P fertilization rather than direct addition of Cd . For a single or few applications, Cd addition will be insignificant compared with total volume of receiving soil but repeated application may lead to a gradual buildup of Cd in agricultural soils over time . In long-term field studies in USA, UK and Norway, no significant change in the Cd content of soils was found from the application of phosphorus fertilizer . However, researchers in Australia and the U.K. reported that long-term applications of P fertilizers increased concentration of Cd in surface soil [15,16]. Increased Cd accumulation in oat, ryegrass, carrot, and spinach was reported in response to the application of P or NPK fertilizer containing 1 to 400 mg Cd kg-1 P .
Assessing the impact of phosphate fertilization on the accumulation of Cd in soils and its transfer to plants requires adequate knowledge of how various factors affect Cd phytoavailability. Soil properties that can influence Cd availability include pH, clay type, chloride content and the content of soil organic matter and Fe and Mn oxides . Of these soil properties, soil pH is often the most important factor in regulating the availability of Cd in soil and its uptake by plants [11,19]. However, increasing soil pH does not always reduce Cd availability in soils and plant uptake, because this relationship depends on other factors such as soil characteristics, plant species and field conditions . Singh et al.  found that the decrease in Cd concentration was not consistent at pH levels beyond 6.5. Besides the soil and plant factors, the field conditions can change the Cd availability to plants, due to a better plant root system induced by liming or environmental conditions .
The impact of P fertilization has mostly been evaluated under growth chamber studies and relatively few information are available on long-term effects of repeated application of Cd through P fertilizers. The hypothesis is that i) long-term use of Cd-rich P- fertilizers increase the total and labile concentrations of Cd in soil, and ii) that the uptake of Cd have increased as a function of the long-term applications of Cd rich P to soils. Hence, a long-term experiment was conducted at the experimental farm of the Norwegian University of Life Sciences Ås, southeastern Norway. This area is one of the most productive Norwegian agriculture regions, and is characterized by slightly acid soils. The study was designed to investigate the effect of P fertilizers containing varying amounts of Cd, based on the origin of rock phosphate, on total and extractable Cd in soils and its uptake by plants at different pH levels during a period of 15 years under field conditions.
Materials and Methods
A long-term fertility experiment was initiated in 1992 at the experimental farm of Department of Environment Sciences, Norwegian University of Life Sciences, Ås, on a loam soil (39% sand, 40% silt and 21% clay), classified as Fluventic Humaquept . The soil contained 2.4% organic carbon, 0.19 mg Cd kg-1 and 82 mg extractable P kg-1. Prior to initiation of this experiment, the field was used for a liming experiment with different pH levels over a long period. The cadmium (Cd) experiment was imposed on this liming experiment. The experiment was a factorial randomized block design with 18 plots (2 replicates, 3 initial pH levels and 3 Cd-treatments). Each plot was 4.5 m × 10 m=45 m2, with the harvesting area of 2 × 8=16 m2. Before conducting the experiment, the plots were treated with lime (dolomite 31.5 %) to achieve soil pH1=5.0 (no lime), pH2=5.6 and pH3=6.0. However, that pH range not successfully obtained (Table 1). The liming was thus repeated during the course of the study to keep the pH levels near to the initial values set. . Phosphorus fertilizers were applied at the rate of 30 kg ha-1 and three different NPK fertilizers with different Cd concentration were used. The first fertilizer (NPK with 17%, N 5% P, and 13%K) contained 1 mg Cd kg-1 P, and supplied about 0.03 g Cd ha-1 yr-1. The second fertilizer (15% N, 15%P, and 15% K) contained 90 mg Cd kg-1 P and supplied 2.7 g Cd ha-1 yr-1 and the third fertilizer (15% N, 15% P, and 15% K), contained about 381 mg Cd kg-1 P and supplied 11.43 g Cd ha-1 yr-1. YARA Norge AS, based on rock phosphate of different origins, manufactured these fertilizers. All fertilizers were applied as basal dose before sowing oat.
|DOC (mg l-1)||115 (29.9)||112 (32.1)||36 (5.8)|
|P-AL, (mg kg-1)||82||91|
|PO43- (mg kg-1)||0.17 (0.06)||0.15 (0.02)||0.12 (0.01)|
|CEC (1M NH4AC):|
|Ca+2 (mg kg-1)||4.9||7.3|
|Mg+2 (mg kg-1)||0.62||0.87|
|Na+ (mg kg-1)||0.05||0.09|
|K+ (mg kg-1)||0.3||0.5|
Table 1: Chemical properties of soil collected in 1992, 1995 and 2006.
Collection of soil and plant sample
The surface soil samples (0-20 cm) for this study were collected from three years 1992,1995 and 2006, while those of grain samples from five years 1992, 1995, 1997, 2002 and 2006. In each plot, 6-8 subsamples were collected from 0-20 cm depth with soil auger, which were made into a composite sample. During soil sampling, a grid pattern with Zig-Zag line was followed so that the composite sample represents the entire plot. This stratified random method increases the precision for the field as well as it increases the accuracy of soil tests. This composite sample was then air dried, ground and passed through a 2 mm sieve prior to analysis. Crop harvested at maturity was separated into grain and straw but only grain samples were used for Cd analysis.
Soil samples were analyzed for “total” and extractable Cd, cation exchange capacity, dissolved organic carbon, PO43- and soil pH as described below.
Total and extractable Cd: Estimation of the apparent total concentration of Cd in soil (from now on coined total Cd) was conducted after decomposing the soil by concentrated strong acid as outlined here: 1 g of soil sample was placed into a Teflon tube with 5 ml of freshly sub boiled ultra-pure nitric acid, and the digestion was performed with an Ultra clave. The start pressure was 50 bars and the Ultra clave temperature was 250ºC for about 25 minutes. The digested samples were diluted to 50 ml by adding double de-ionized water. The same soil samples were also extracted with 30 ml of 0.01M NH4NO3, having soil solution ratio of 1:10. This solution was mixed with 3 g of soil and shaken overnight. The next day, the solution was centrifuged for 30 min. The suspension was passed through a Blue Ribbon (diameter 125 mm) filter, and kept overnight at room temperature. The concentration of Cd in the digested and extracted solutions was determined by ICPMS (Perkin Elmer Sciex Elan 6000) using Rh (Rhodium) as internal standard. Here, we use the term extractable Cd for NH4NO3 extractable Cd.
Soil chemical parameters: For the determination of dissolved organic carbon (DOC) and phosphate ions (PO43-), soil samples were extracted with 30 ml of 0.01 M KNO3, having a soil solution ratio of 1:10. The suspensions were filtered through “Blue ribbon” filters and the PO43- ions in filtrates were determined by a Lachate IC500 Ion Chromatography analyzer. For the determination of DOC, the filtrates were passed through 0.45 μm membrane filters and analyzed by a Shimadzu TOC-V analyzer with Pt-catalyzed combustion. Experimental blanks were provided. Soil pH was measured at a soilwater ratio of 1:2.5 w/v by glass electrode (Orion pH-instrument model SA 720 with combination pH electrode) . 1M ammonium acetate (NH4AC) at neutral pH was used to determine soil cation exchange capacity (H+, Ca2+, K+, Mg2+, and Na+) (CEC). Three g of soil was mixed with 20 ml of 1 M NH4AC and shaken on an end over end shaker overnight. The next day, the suspension was passed through a Blue Ribbon (Dia 125 mm) filter, and made to 25 ml with NH4AC . The extracted solution was analyzed for cations by using an ICP-OES analyzer (Perkin Elmer, Optima 5300 DV) and H+ by titration with NAOH.
Analysis of plant samples
To determine dry matter yield, grain samples were oven dried at 105ºC and weighed. The grain samples were digested by dry-ashing the plant samples at 450ºC with treatment of 1:2 conc. HCL: HNO3 mixture. The heating and acid digestion step was done twice and the collected residue was then dissolved in 5 ml of HNO3 and finally diluted to 50 ml by double distilled water prior to analysis of Cd by an ICPOES analyzer (Perkin Elmer, Optima 5300 DV).
The speciation of Cd in the 0.01M NH4NO3 extracts was calculated using WHAM/Model VII version 7.0.4 for waters . Input values (Cd, pH, DOC, PO43-), are shown in Tables 1 and 2. The 0.01 M concentrations of NH4+ and NO3- from the extract solution was also included. We treated the system as being in equilibrium with the atmosphere (p CO2=3.9 × 10-4atm.). We also assumed dissolved organic matter (DOM) to have the ion binding properties of ‘default’ fulvic acid, FA, as defined in WHAM/Model VI, and that the DOM is 50% carbon by weight. As suggested by the software guide, we let 50% of the acid groups of FA being active in proton/metal binding. The free ion activity of (FIA) Cd or Cd bound to dissolved organic matter (DOM) is quoted as Cd-FIA and Cd-DOM, respectively.
All statistical analysis were conducted using JMP Pro v 13.0.0 . The models included were analysis of variance, stepwise-, linear- and multiple regression. The level of statistical significance relative to P values is hereafter referred to as P <0.05 or P> 0.05, being statistically significant or non -significant, respectively.
Results And Discussion
Total and extractable Cd concentration
The liming treatments had forced the soil pH to near the three desired levels, but soil pH increased slightly with years (Table 1). At least in the most acid soils. Although the Cd-application rates increased with two folds from lowest to highest, there was no significant increase in CdHNO3 (“total”) before 2006 (Table 2). Neither within treatments nor as compared to the inherent CdHNO3 before initiation of experiment (0.19 mg/kg). In soils from 2006, the repeated application rates had created a minor, but corresponding increase with the CdHNO3. The little effect of Cd input on soil Cd (total or extractable) is partly assigned to relatively minor contribution of Cd input (0.03-11.43 g/ ha), and from the literature, the effect of low application rates of Cd to cultivated soils vary. Jeng and Singh  found only minor changes in Cd content of soil samples from the treated plots with organic and inorganic fertilizers during a long-term experimental period from 1963 to 1991. The results reported by Sato et al.  and Meers et al.  also support this finding. Others have reported some increase of Cd resulting from long-term applications of Cd-rich P-fertilizers. In a long-term mineral fertilization experiment carried out in Germany, it was found that aqua-regia extractable Cd in soils increased due to long-term application of commercial fertilizer as compared to control plots . Similarly, Loganathan et al.  and Gray et al.  found marked increase in acid-extractable Cd in surface soils after long-term fertilization in pasture systems in New Zealand. From a greenhouse experiment, He and Singh  reported that increasing the Cd input from 2,7 μg Cd kg-1 soil to 12,5 μg Cd kg-1 soil through P fertilizers, resulted in an increase in acid-extractable Cd in a loam soil from 18,7 μg Cd pot-1 soil to 87,0 μg Cd pot-1 .
g ha-1 y-1
|CdHNO3 (mg/kg)||0.03||0.17 (± 0.01)||0.19 (± 0.01)||0.19 (± 0.02)|
|2.70||0.19 (± 0.01)||0.19 (± 0.01)||0.21 (± 0.01)|
|381||0.17 (± 0.01)||0.18 (± 0.01)||0.22 (± 0.02)|
|CdNH4NO3 (μg/kg)||0.03||7.0 (± 5.6)||8.1 (± 7.5)||4.3 (± 3.0)|
|2.70||6.6 (± 5.4)||8.3 (± 7.5)||3.8 (± 3.3)|
|381||7.0 (± 5.5)||7.5 (± 6.7)||5.6 (± 4.2)|
Table 2 : Cadmium in soil and soil extracts in 1992, 1995 and 2006. The inherent CdHNO3 was 0.19 mg/kg before initiation of experiment (Std.dv. are shown, n=6).
The NH4NO3- extractable Cd (CdNH4NO3-) in our field trial was controlled by other factors than the application rates, and most evident is the pH. Even if it seems from Table 2 that the CdNH4NO3- in 2006 is controlled by the application rates, the statistical tests show a very strong correlation with pH for that year. The pH was negatively correlated with CdNH4NO3- in 1992 (r2=0.88, p<0.001) and 2006 (r2=0.89, p<0.001), but not correlated in 1995. Such pH-effect have also been reported by Wang et al. , who found significant increase of extractable Cd with decrease in soil pH for plant Thalspi caerulescens. Similar results have been reported by several others [19,32,33]. The positive and nonsignificant relationship between NH4NO3- extractable Cd and Cd input through fertilizers have earlier been reported [14,34-36]. The year 1995 was an exceptional year, with for instance very high plant yield (Table 3), and for that year the DOC was positively correlated with CdNH4NO3- , (r2=0.71, p<0.001). The DOC extracted from the 1995 soils was, however, not exceptionally high compared to 1992 sampling. It can be seen in Table 1 that the DOC is remarkably much lower in 2006 compared to 1992 and 1995, and the concentrations of CdNH4NO3- were reduced to almost half compared to the earlier samplings. This is partly related to the increased pH in 2006 and possibly the low DOC. A combined regression model containing pH and DOC described 42% of the variation in CdNH4NO3- significantly (p<0.001) across the three years, where pH is negatively related and DOC positively related to CdNH4NO3- . From a batch titration study conducted by Almås et al. , the same solubility controlling mechanisms were observed and described by WHAM/Model VI  making use of a parameterized version of the SCAMP sub-model . These were mostly cultivated soils, and the solution pH was controlled by an active soil Ca pool (soils were frequently limed). When the pH control was optimized, the soluble cations were mostly well predicted. Moreover, the optimized model predicted solid phase metals predominantly bound to soil organic matter and insignificantly to clays and iron/aluminum oxides. We assume that the same mechanisms control Cd solubility in this field trial as both pH and DOC plays a role.
|pH treatment level||Grain yield kg ha-1|
|5.0||773 (± 54)||na||2972 (± 333)||2614 (± 58)||1188 (± 40)|
|5.6||1178 (± 137)||4628 (± 209)||3383 (± 206)||2855 (± 109)||1247 (± 33)|
|6.0||1027 (± 60)||4973 (± 13)||3046 (± 76)||2589 (± 219)||1127 (± 24)|
Table 3 : Long -term pH-effect on grain yield of plant in different years (Std.dv. are shown, n=6).
Except from the harvest in 1995, for all the other years plants were harvested, pH treatment 5.6 resulted in the highest grain yields (Table 3). In general, grain yield increased from year 1992 to 1995 and then it decreased significantly from 1995 to 2006. There was no significant difference comparing grain yields of 1992 with 2016. The Cd treatment had no significant effect on yield and hence annual yields are grouped for each pH treatments. Grant et al.  also did not find any effect of moderate Cd applications on grain yield of durum wheat or flax. The exceptional high yield in 1995 was compared with meteorological data from the area, and generally was the summer 1992 dry (average 2.0 mm during June and July) and temperature low during growth season (June and July, oscillating around 16.8°C). In 2006 the precipitation (average 1.7 mm during June and July) was less than in 1995 (average 4.8 mm during June and July). It seems, however, to be important that in 1995 there were frequent episodes of short but heavy summer rain (episodes of 20, 40 to 80 mm/day) during June and July. Those heavy summer showers have likely humidified the whole root zone better, resulting in higher yields. Average temperature in 1995 and 2005 were 15.3°C and 17.2°C, respectively.
Plant cadmium concentration
Increase in Cd input through fertilizers from 0.03 g/ha/yr to 11.43 g/ha/yr did not significantly affect the Cd concentration in plant within the trial period (Table 4). Neither did the application doses affect the uptake. The lack of direct relationship between moderate Cd application to soil and uptake in plants have also been reported by others [32,36,39-41]. Guttormsen et al.  did however, report significant increase of plant Cd concentration with increase in Cd input, using the same range of Cd input through P fertilizers. In that experiment, however. Perriguey et al.  found increased Cd concentration in roots of maize plant with increasing concentrations of Cd in nutrient solution. The transport to the rest of the plant was not affected equality. The phytoavailability of Cd in soil depends upon the plant species  and its physiological status [45,46], but also on the geochemistry of Cd in soil solution and the ability of the solid phase to replenish Cd removed from soil solution during the plant uptake period. The geochemistry of trace metals in soils are mostly controlled by the pH, soil organic material (SOM) and OC, whereas the level of concentration is determined by the inherent total concentration in soil [37,47-49].
|Input Cd (g ha-1 y-1)||Plant Cd (mg kg-1)|
|0.03||0.12 (± 0.015)||0.04 (± 0.014)||0.06 (± 0.016)||0.03 (± 0.013)||0.03 (± 0.009)|
|2.7||0.09 (± 0.032)||0.03 (± 0.007)||0.05 (± 0.02)||0.03 (± 0.014)||0.02 (± 0.009)|
|11.43||0.09 (± 0.026)||0.03 (± 0.011)||0.07 (± 0.02)||0.03 (± 0.018)||0.03 (± 0.011)|
Table 4: Relationship between Cd in oat grain and Cd input in different years (Std.dv. are shown, n=6).
The statistical relationship between concentration of Cd in plant, yield and some geochemical parameters was tested. These were pH, DOC, Cd-FIA, Cd-DOM, CdHNO3, CdNH4NO3-, and PO43-. Yield was very different between years and the total uptake, or offtake, is higher in years of good yield (all three years, r2=0.50, p<0.0001). Soil pH is a major factor influencing Cd solubility and mobility in soils. Cd Solubility and ion activity decreases with increasing pH that finally increases Cd sorption. Therefore, the soil distribution coefficient (Kd), increases with increasing pH, while phytoavailability correspondingly decreases [50,51]. Low soil pH contribute to greater plant availability of the Cd present in the soil . Since pH is an important factor controlling the geochemistry of Cd, pH was tested against Cd uptake. The relationship was insignificant for all years, and significantly negative only for the 2006 year data (r2=0.82, p<0.0001). After an initial stepwise regression exercise containing the above mentioned parameters, we tested a multivariate regression model on the Cd uptake. The uptake was controlled by yield, pH and DOC (r2=0.75, p<0.0001). When the exceptional year 1995 was removed from the date, yield and DOC were still significantly controlling the uptake (r2=0.68, p<0.0001). Since however, uptake is the product of yield and concentration, the Cd uptake was tested without yield, and then pH and DOC in combination explained about 57% of the variation in Cd uptake. The most significant parameter was DOC (r2=0.47, p<0.0001) all the three years included. When every year was investigated separately, yield was always the most significant parameter. One year in company with pH (1992), or PO43- (1995) or FA-Cd (2006). In 2006, the combination of FA-Cd and yield did in fact explain 92% of the Cd-uptake. In sum for this soil type, the yield seems to be the most important factor controlling the Cd uptake from a soil amended with moderate amounts of Cd through inorganic fertilizer. McLaughlin et al.  reported that Cd concentrations in potato tubers were positively related to the degree of Cd-Cl complexes in solution. Despite that Cd form complexes with Cl, the Cl concentrations in soil solution in this soil are too low to have an impact as there is an excess of rain water preventing accumulation of Cl in the root zone. Increase in soil pH decreased plant cadmium concentration. These results are in accordance with those reported by several investigators [34,42,53]. Ciecko et al.  reported ten folds decrease in plant Cd concentration with liming in their experiment on Triticale and oil rapeseed.
The same three doses of Cd concentration (0.03, 2.7 and 11.43 g/ ha) were applied through P fertilizer during 15 years of the experiment. The observed changes in total and extractable Cd in the soil and concentration and uptake of Cd in plant during the entire experimental period are described below.
Changes in total and extractable Cd concentration in soil
Total cadmium concentration varied differently during the experimental years for each Cd treatment. At the application rate of 11.43 Cd g ha-1, an increase in total Cd concentration was observed throughout the experimental period. However, at the rate 2.7 g Cd ha-1, total Cd decreased in 1995 but increased in 2006, while in the control treatment (0.03 g ha-1) total Cd increased consistently despite at a much lower rate (Figure 1). Cadmium enrichment in soils through mineral fertilizers is reported in the literature. Loganathan et al.  and Gray et al.  reported that the long-term (10-47 years) application of phosphate fertilization to pasture systems in New Zealand caused a significant increase in total Cd in soils. Similarly, Czarnecki and During  found that pseudo total and mobile concentration of metals (Cd, Cu, Pb and Zn) increased in soils due to application of 14 years of mineral fertilizer application as compared to control plots.
A slight increase in extractable Cd was observed in 1995 as compared to 1992 for the Cd input rates of 2.7 and 11.34 but the concentration decreased in all Cd treatment in 2006. Availability of the applied Cd may be attenuated over time by various aging processes. In a growth chamber study, Hamon et al.  reported that in the soils, where Cd application was terminated after 27 years of mineral fertilizer application, 40% of the added Cd over time was in plant available form , while in the soil where Cd application was still continuing (47 years after) about 72% of the Cd was in plant available form. The decrease in availability between the continuous and rundown plots indicates that stabilization processes occurring overtime decreased the availability of Cd added to the soil. This stabilization may provide a partial explanation for the lack of consistent trend in increasing Cd availability over time with repeated application of Cd in mineral fertilizer.
Change in Plant Cd concentration and uptake
Cadmium concentration in oat crop decreased during the period of 1992-1995 and then increases from 1995-1997, being highest in 1997 and then it decreases until 2006 (Figure 2). The differences in Cd among the years were significant (p<0.05). There were minor changes in plant Cd concentration with increased Cd input. Although year to year variability in plant Cd concentration could be associated with dilution/ concentration effect as observed by Grant et al.  where the highest annual Cd concentration in the control treatments was associated with the lowest annual grain yield. This seems not to be the case in the present study because control plots with generally lower yield (Table 3) showed higher Cd concentration. In addition, the year 1992 with lowest yield in all the years showed much higher plant Cd concentration. However, as stated above, attenuation in Cd availability with time may be partly responsible for this variability.
Increase in soil pH decreased plant Cd concentration significantly in all the years. Such relationship between soil pH and plant Cd has been widely reported in the literature [19,31-33,56]. Wang et al.  reported that the extractable Cd increased with lowering of soil pH and resulted in enhancing phytoextraction. Reiser et al.  also showed that soil pH , soil Fe and soil Cd provided an excellent predictor of the Ca (NO3)2 –extractable soil Cd fraction, but they explained just 38 % of the variation of Cd concentration in pasture grasses.
Long-term use of phosphorus fertilizers containing Cd is of greater concern because of danger associated with its build up in soils and further transfer to food chain. Thus, the major objective of this experiment was to assess the effect of Cd input and soil pH on the availability of Cd to plant. Cd input through fertilizers showed no significant effect on either plant Cd or soil Cd. Hence, we can conclude that plant Cd as well as soil Cd did not change over time at the rates of Cd added within the range used in this experiment. However, soil pH generally showed negative effect on Cd uptake and its availability to oat plant throughout the experimental period. Due to occasional (every 4th or 5th year) liming, soil pH was increased over 14 years leading to decreased plant Cd uptake and soil Cd concentration. Beside soil pH, grain yield also affected Cd uptake by oat plant as higher yield resulted in higher Cd uptake.
Model (WHAM) prediction of Cd uptake by plants showed that crop yield, pH and DOC in combination explained about 57% of the variation in Cd uptake and DOC (r2=0.47, p<0.0001) was the most important factor. However, in individual years (e.g. 2006) the combination of FA-Cd and yield did in fact explain 92% of the Cd-uptake. A slight increase in extractable Cd in soil was observed after continuous fertilization. Since there was no significant effect of the rate of soil Cd application on the yield and plant Cd uptake, the long-term use of Cd enriched P-fertilizers increased the total concentration of soil Cd slightly. Even though soil Cd concentration increased with increase in Cd enriched phosphorus fertilizer, its bioavailability depended more on soil pH rather than Cd input through fertilizers.
- Grant CA, Clarke JM, Duguid S, Chaney RL (2008) Selection and breeding of plant cultivars to minimize cadmium accumulation. Science Total Environ 390:301-310.
- Huang, B, Kuo S, Bembenek, R (2004) Availability of cadmium in some phosphorus fertilizers to field-grown lettuce. Water Air Soil Poll 158: 37-51.
- Sheppard SC, Grant CA, Sheppard MI, Jong R, Long J (2009) Risk indicator for agricultural inputs of trace elements to Canadian soils. J Environ Qual 38: 919-932.
- Grant CA (2011) Influence of phosphate fertilizer on cadmium in agricultural soils and crops. Pedologist 143-155.
- Chen WP, Krage N, Wu LS, Page, A Chang AC (2008) Fertilizer application and heavy metal contents in vegetable production soils of California. Water Air Soil Poll 190: 209-219.
- McLaughlin MJ, Singh BR (1999) Cadmium in Soils and Plants. Dordrecht, The Netherlands: Kluwer Academic Publisher
- Vig K, Megharaj M, Sethunathan N Naidu R (2003) Bioavailability and toxicity of cadmium to microorganisms and their activities in soil. Advances in Environmental Research 8: 121-135.
- Grant CA, Flaton D, Tenuta M, Mahli S, Akinremi, W (2013) The effect of rate and Cd concentration of repeated phosphate fertilizer applications on seed Cd concentration varies with crop and environment. Plant Soil 372: 221-233.
- Jiao W, Chen W, Chang,AC, Page, AL (2012) Environmental risks of trace elements associated with long-term phosphate fertilizers applications: A review Environmental Pollution 168: 44-53.
- Sheppard MI, Sheppard SC, Grant CA (2007) Solid/liquid partition coefficients to model trace element critical loads for agricultural soils in Canada Can J Soil Sci 87: 189-01.
- Grant CA, Bailey LD, Mc Laughlin MJ, Singh BR (1999) Management factors which influence cadmium concentrations in crops. Cadmium in soils and plants pp: 151-198.
- Gao X, Tenuta M, Flaten DN, Grant CA (2011) Cadmium concentration in flax colonized by mycorrhizal fungi depends on soil phosphorus and cadmium concentrations. Communications in Soil Science andPlant Analysis 42: 1882-1897.
- Chen L, Guo, Y, Yang L, Wang Q (2007) SEC-ICP-MS and ESI-MS/MS for analyzing in vitro and in vivo Cd-phytochelatin complexes in a Cd-hyperaccumulator Brassica chinensis. J Anal Spectrom 22: 1403-1408.
- Jeng AS, Singh BR (1995) Cadmium status of soils and plants from a long-term fertility experiment in southeast Norway. Plant Soil 17: 67-74.
- Nicholson FA, Jones KC, Johnston AE (1994) Effect of phosphate fertilizers and atmospheric deposition on long-term changes in the cadmium content of soils and crops. Environ Sci Technol 28: 2170-2175.
- Loganathan P, Mackay AD, Lee J, Hedley MJ (1995) Cadmium distribution in hill pastures as influenced by 20 years of phosphate fertilizer application and sheep grazing. Aust J Soil Res 33: 859-871.
- He QB, Singh BR (1994) Crop uptake of cadmium from phosphorus fertilisers, I. Yield and cadmium content. Water Air Soil Pollut 74: 251-265.
- McLaughlin MJ, Hamon RE, McLaren RG, Speir TW, Rogers SL (2000) Review: A bioavailability based rationale for controlling metal and metalloid contamination of agricultural land in Australia and New Zealand. Aust J Soil Res 38: 1037-1086.
- Singh BR, Narwal RP, Jeng AS, Almås Å (1995) Crop uptake and extractability of cadmium in soils naturally high in metals at different pH levels. Commum soil science Plant analysis 26: 2123-2142.
- He QB, Singh BR (1993) Plant availability of Cd in soils. I. Extractability of Cd in newly- and long-term cultivated soils. Acta Agr Scand 43: 134-141.
- Soil Survey staff (1999) Soil Taxonomy, USDA Handbook No. 436, Washington DC
- Mc Lean EO (1982) Soil pH and Lime Requirement. IN: Page AL (ED) Methods of Soil Analysis Part 2, ASA, Madison.
- Schollenbergen CJ, Simon RH (1945) Determinative exchange capacity and exchangeable bases in soil ammonium acetate method. Soil Science 59: 13-24.
- Tipping E (1998) Humic ion-binding Model VI: An improved description of the interactions of protons and metal ions with humic substances. Aquatic Geochemistry 4: 3-47.
- SAS-Institute JMP (2016) Statistical Discovery Software, v 13.0.0, 13.0.0; SAS Institute, Inc.: Cary, NC, USA.
- Sato A, Takeda H, Oyanagi W, Nishihara E, Murakami M (2010) Reduction of cadmium uptake in spinach (Spinacia oleracea L.) by soil amendment with animal waste compost. Journal of Hazardous Materials 181: 298-304.
- Meers E, Laing GD, UnamunoV, Ruttens A, Vangronsveld J, et al. (2007) Comparison of cadmium extractability from soils by commonly used single extraction protocols. Geoderma 141: 247-259.
- Czarnecki S, During RA (2015) Influence of long –term mineral fertilization on metal contents and properties of soil samples taken from different locations in Hesse, Germany. Soil 1: 23-33.
- Loganathan P, Hedley MJ, Gregg PEH, Curie LD (1997) Effect of phosphate fertilizer type on the accumulation and plant available Cd in Grassland soils. Nutr Cycl Agroecosys 47: 169-178.
- Gray CW, McLaren RG, Roberts AHC, Condron IM (1999) The effect of long-term phosphatic fertilizer applications on the ammounts and forms of Cd in soils under pastures in New Lealand. Nutr Cycl Agroecosys 54: 267-277.
- Wang G, Su MY, Chen YH, Lin FF, Luo D, et al. (2006) Transfer characteristics of cadmium and lead from soil to the edible parts of six vegetable species in southeastern China. Environmental Pollution, 144: 127-135.
- Gao X, Grant CA (2012) Cadmium and zinc concentration in grain of durum wheat in relation to phosphorus fertilization, crop sequence and tillage management. Applied and Environmental Soil Science 10.
- Jiao Y, Grant CA, Bailey LD (2004) Effects of phosphorus and zinc fertilizer on cadmium uptake and distribution in flax and durum wheat. J Sci Fd Agric 84: 777-785.
- Singh BR, Myhr K (1998) Cadmium uptake by barley as affected by Cd sources and pH levels. Geoderma 84: 185-194.
- Lambert R, Grant CA, Sauve S (2007) Cadmium and zinc in soil solution extracts following the application of phosphate fertilizers. Sci Total Environ 378: 293-305.
- Grant CA, Sheppard SC (2008) Fertilizer impacts on cadmium availability in agricultural soils and crops. Human and ecolog. risk assessment 14: 210-228.
- Almås ÅR, Lofts S. Tipping E, Mulder J (2007) Solubility of major cations and Cu, Zn and Cd in soil extracts of some contaminated agricultural soils near a zinc smelter in Norway: Modeling with a multi-surface extension of WHAM. Eur J Soil Sci 58: 1074-1086.
- Lofts S, Tipping E (1998) An assemblage model for cation binding by natural particulate matter. Geochim Cosmochim Acta 62: 2609-2625.
- Grant CA, Monreal MA, Irvine RB, Mohr RM, McLaren DL, et al. (2009) Crop response to current and previous season applications of phosphorus as affected by crop sequence and tillage, Canadian Journal of Plant Science 89: 49-66.
- Kashem MA, Singh BR (2002) The effect of fertilizer additions on the solubility and plant-availability of Cd, Ni and Zn in soil. Nutr Cycl Agroecosys 62: 287-296.
- Gao X, Akhter F, Tenuta M, Flaten DN, Gawalko EJ, et al. (2010) Mycorrhizal colonization and grain Cd concentration of field-grown durum wheat in response to tillage, preceding crop and phosphorus fertilization. J Sci Fd Agric 90: 750-758.
- Guttormsen G, Singh R, Jeng AS (1995) Cadmium concentration in vegetable crops grown in a sandy soil as affected by Cd levels in fertilizer and soil pH. Fertilizer Res 41: 27-32.
- Perriguey J, Sterckeman T, Morel JL (2008) Effect of rhizosphere and plant-related factors on the cadmium uptake by maize. Environmental and Experimental Botany 63: 333-341.
- Almås ÅR, Lombnæs P, Sogn TA, Mulder J (2006) Speciation of Cd and Zn in contaminated soils determined by DGT-DIFS, and WHAM Model/ VI in relation to uptake by spinach and ryegrass. Chemosphere 62: 1647-1655.
- Manousaki E, Kalogerakis N (2009) Phytoextraction of Pb and Cd by the Mediterranean saltbush (Atriplex halimus L.): Metal uptake in relation to salinity. Environ Sci Pollut Res 16: 844-854.
- Shi GR, Xia SL, Ye J, Huang YN, Liu CF, et al. (2015) PEG-simulated drought stress decreases cadmium accumulation in castor bean by altering root morphology. Environ Exp Bot 111: 127-134.
- Ivezic V, Almås ÅR, Singh BR (2012) Predicting the solubility of Cd, Cu, Pb and Zn in uncontaminated Croatian soils under different land uses by applying established regression models. Geoderma 170: 89-95.
- Sauve S, Norvell WA, McBride M, Hendershot W (2000 a) Speciation and complexation of cadmium in extracted soil solutions. Environ Sci Technol 34: 291-296.
- Tipping E, Rieuwerts J, Pan G, Ashmore MR, Loft S, et al. (2003) The solid solution partitioning of heavy metals (Cu, Zn, Cd, Pb) in upland soils of England and Wales. Environmental Pollution 125: 213-225.
- Sauvé S, Hendershot W, Allen HE (2000) Solid-solution partitioning of metals in contaminated soils: Dependence on pH, total metal burden, and organic matter. Environmental Science & Technology 34: 1125-1131.
- Rieuwerts JS, Ashmore MR, Farago ME, Thornton I (2006) The influence of soil characteristics on the extractability of Cd, Pb and Zn in upland and moorland soils. Sci Total Environ 366: 864-875.
- McLaughlin MJ, Tiller KG, Smart MK (1997) Speciation of cadmium in soil solutions of saline/sodic soils and relationship with cadmium concentrations in potato tubers (Solanum tuberosum L). Australian Journal of Soil Research 35: 183-198.
- Mench H, Baize D, Mocguot B (1997) Cadmium availability to wheat in five soil series from the Y onne district, Burgundy, France. Environmental Pollution 95: 93-103.
- Ciecko Z, Wyszkowski M, Krajewski W, Zabielska J (2001) Effect of organic matter and liming on the reduction of cadmium uptake from soil by triticale and spring oilseed rape. Science of the Total Environment 281: 37-45.
- Hamon RE, McLaughlin MJ, Naidu R, Corell R (1998) Long-term changes in Cd availability in soil. Environ Sci Technol 32: 3699-3703.
- Reiser R, Simmler M, Portmann D, Clucas L, Schulin R, et al. (2014) Cadmium concentration in New Zealand pastures: Relationships to soil and climate variables. J Enviro Qual 43: 917-925.
Citation: Singh BR, Dependra KC, Åsgeir RA (2017) Long-Term Effect of Phosphate Fertilization on Cadmium Uptake by Oat and its Accumulation in Soil. J Environ Anal Toxicol 7: 516 Doi: 10.4172/2161-0525.1000516
Copyright: © 2017 Singh BR, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
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