©2007 Poultry Science Association, Inc. Water Extractable Trace Elements in Poultry Litters and Granulated Products G. S. Toor,*1 B. E. Haggard,† and A. M. Donoghue‡ *Soil and Water Science Department, Gulf Coast Research and Education Center, Wimauma, FL 33598; †Biological and Agricultural Engineering, University of Arkansas, Fayetteville 72701; and ‡USDA-ARS Poultry Production and Product Safety Research Unit, Fayetteville, AR 72701 SUMMARY Poultry litter contains many trace elements such as As, Cu, and Zn, and its land application may lead to the accumulation of these elements in soils, especially near the soil surface. The objectives of this study were to determine the total amount of trace elements and evaluate the effect of litter granulation and various litter to water extraction ratios on water extractable trace elements in 8 raw and granulated litter products. Granulated litters that contained urea, dicyandiamide, or hydrolyzed feathermeal had significantly lower contents of total As, B, Cu, Mn, and Zn than untreated litters because of the dilution of litters with additives. Trace element concentrations (mg/L) in the water extracts of the various poultry litters generally decreased when extraction ratios (litter to water) shifted from 1:10 to 1:250, or as the amount of poultry litter decreased with a constant water volume (200 mL). But, the water extractable content of trace metals (mg/kg) generally increased from an extraction ratio of 1:10 to 1:200, with values similar at 1:200 and 1:250 extraction ratios. Based on our results, we suggest using a 1:200 extraction ratio when evaluating water extractable As, Cu, and Zn in poultry litters. The estimated land application rates of trace metals, when poultry litter is applied on the basis of total P content, were considerably lower than the trace metal loadings allowable under the current environmental regulations governing biosolids and other materials with measurable amounts of trace metals. The laboratory water extractions of poultry litters and granulated products have increased our understanding of the potential risks to water quality posed by the land application of poultry litter and will contribute to the development of base knowledge needed to define land application practices that are protective of soil and water quality. Key words: poultry litter, granulation, water extractable trace element, litter water extraction, arsenic, copper, zinc 2007 J. Appl. Poult. Res. 16:351–360 DESCRIPTION OF PROBLEM United States Environmental Protection Agency Part 503 rule [1] regulates the application of biosolids based on the total contents of As, Cd, Cu, Hg, Mo, Ni, Pb, Se, and Zn. For instance, 1 Corresponding author: [email protected] the application of biosolids to soil should not add greater than 2, 75, and 140 kg/ha per yr of As, Cu, and Zn, respectively. Recently, litigation in Arkansas and Oklahoma has targeted the land application of poultry litters and specifically identified several trace elements in poultry litter, (i.e., Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 Primary Audience: Environmental Managers, Nutritionists, Poultry Producers, Researchers 352 might be used. Therefore, our objectives in this study were (i) to determine the total amount of trace elements in raw/ground poultry litters and granulated poultry litter products, (ii) to evaluate the influence of poultry litter to water extraction ratios on the measure of soluble trace elements in the poultry litters and granulated products, and (iii) to estimate the loading rate of trace elements to soil when these litters and granulated products are land applied on the basis of their total P contents. MATERIALS AND METHODS Poultry Litter Collection Poultry litters (mixture of feces and bedding material) were collected from 2 poultry farms in Northwest Arkansas and granulated at facilities located in Pennsylvania and Arkansas. Poultry litter from 1 farm near Decatur, AR, was ground to pass through a 5.8-mm mesh screen and thoroughly mixed using a New Holland 352 feed mill mixer [14]. The ground and mixed poultry litter was delivered to Mars Mineral Inc. (Mars, PA) and was placed in a holding bin. Feed grade urea [15] and dicyandiamide (DCD) [16] were placed in an adjacent bin and used during the process to produce some of the granulated products. The poultry litter (and additives) were fed into a bench scale granulator [17] with vibrating screw feeders [18]; water was used as the binding agent in the granulation process. After granulation, granulates were moved to a vibrating fluid bed dryer at 232°C and dried to 121°C. Dried granulates were screened to pass through a 4.75-mm mesh screen, but not a 0.85-mm mesh screen. Five treatments resulted from this litter source: 1) raw poultry litter (raw litter no. 1); 2) ground poultry litter (ground litter no. 1); 3) granulated poultry litter (granulated litter no. 1); 4) granulated mixture of poultry litter plus urea (granulated litter no. 1 with urea); and 5) granulated mixture of poultry litter plus urea and DCD (granulated litter no. 1 with urea and DCD). For 100 kg of granulated product, the amount of urea added was 25 kg (25%) for the granulated litter no. 1 with urea, whereas the granulated litter no. 1 with urea and DCD contained 22 kg of urea (22%) and 2.3 kg of DCD (2.3%). Dicyandiamide is a nitrification inhibitor, often used in agricultural practices to reduce nitrate losses [19]. The Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 As, Cu, and Zn) where there are no current regulations on the maximum amount that can be applied to soil. In the United States, animal manures are typically land applied based on P management practices, resulting in the application of measurable amounts of trace elements to soils. For example, Nicholson et al. [2] estimated that animal manure contributes 25 to 40% of the total annual Cu and Zn inputs to soils in the England and Wales. The excessive land application of poultry litter can result in build up of trace elements near the soil surface [3, 4, 5] and can lead to the loss of trace elements to waters through leaching [6, 7] and surface runoff [8]. Van der Watt et al. [9] reported build-up of phytotoxic levels of Cu, Mn, and Zn in soil that received 6 mg/ha per yr of poultry litter for 16 yr. Elevated levels of trace elements are excreted in the manures as the animal diets usually contain trace elements greater than the animal requirements due to the safety margins. The recommended amounts of Cu and Zn in poultry diets are 4 and 50 mg/kg, respectively, whereas Cu and Zn content in poultry diets have been reported to exceed 30 and 100 to 150 mg/kg, respectively [2, 10]. Trace elements are needed to carry out important enzymatic and nonenzymatic functions in the poultry [11, 12]. For example, As has been used in the poultry diets as 3-nitro-4-hydroxyphenylarsonic acid (Roxarsane) or 4-aminophenylarsonic acid (p-ASA) to prevent coccidiosis, increase weight gain, and improve feed efficiency [13]. Similarly, Cu and Zn have been used as growth promoters or biocides in the poultry feed [12, 13]. To manage potential long-term impacts of trace elements in soils, it is important to first quantify total and soluble trace elements in animal manures and then identify soils that are most vulnerable to trace elements loss via surface runoff and leaching. Little information is available on the trace element inputs to soils from today’s animal manures, whose chemical composition may be different from the past manures because animal diets are often changing, driven by animal genetics and variable costs of diet ingredients. At the same time, efforts are underway to balance nutrient (particularly P) inputs and outputs in intensive animal production regions by developing off-farm uses of manures such as in turf, lawn, and gardens where granulated poultry litters JAPR: Research Report 18.3 ± 0.4a 15.5 ± 0.5b 44.9b 60.6a 1 1 with urea 1 with urea and DCD 2 with feathermeal 0.9ab 1.2a 0.9ab 0.4b 1.0c 0.4c 22.7 23.6 22.7 21.9 17.7 16.8 ± ± ± ± ± ± g/kg of DM P 30.6c 31.1c 30.6c 41.5b 141.3a 142.9a N ± ± ± ± ± ± 2a 1a 2a 1a 2b 2b 24 ± 1a 20 ± 1b 43 44 43 41 33 32 As ± ± ± ± ± ± 2a 2a 2a 2a 3b 1b 122 ± 4a 101 ± 2b 69 68 69 66 55 54 B ± ± ± ± ± ± 25b 24a 25b 16b 21c 20c 339 ± 10a 292 ± 6b 599 647 599 591 460 453 Cu ± ± ± ± ± ± 131ab 69ab 131ab 119a 54ab 10b 544 ± 22b 697 ± 23a 561 561 561 636 475 419 mg/kg of DM Fe ± ± ± ± ± ± 3a 20a 3a 7b 19c 22d 453 ± 10a 381 ± 10b 678 688 678 651 575 537 Mn ± ± ± ± ± ± 4b 9a 4b 1b 17c 20.5d 417 ± 14a 364 ± 6b 615 642 615 620 517 490 Zn Source no. 1 Raw litter no. 1 Ground litter no. 1 Heated litter no. 1 Granulated litter no. Granulated litter no. Granulated litter no. LSD (0.05) Source no. 2 Ground litter no. 2 Granulated litter no. LSD (0.05) 2 with feathermeal 1 1 with urea 1 with urea and DCD 870 163 169 106 46 90 5,291 ± 85 4,542 ± 111 224 6,429 ± 7,043 ± 8,029 ± 7,432 ± 4,934 ± 4,839 ± 663 P ± ± ± ± ± ± 6 4.5 2.8 5.0 1.5 3.3 1.6 13 ± 5.8 10 ± 5.6 12 30 28 24 25 20 20 As ± ± ± ± ± ± 9 4.7 4.7 6.6 7.0 3.2 4.1 100 ± 1.9 90 ± 2.8 6 50 53 58 52 45 44 B ± 14.6 ± 1.4 ± 7.5 ± 8.2 ± 3.4 ± 2.7 14 127 ± 1.5 95 ± 1.9 4 244 263 87 243 135 149 mg/kg of DM Cu Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 Poultry litter treatment 4.5 2.3 1.0 3.5 0.3 0.6 13.0 ± 0.3 13.1 ± 0.1 0.1 35 43 54 60 20 18 ± ± ± ± ± ± 5 14 3.7 3.5 3.9 0.8 1.2 ± ± ± ± ± ± 11 54 ± 0.9 42 ± 1.0 2 104 123 52 117 65 68 Mn Fe ± 10.3 ± 3.8 ± 5.1 ± 1.6 ± 1.0 ± 1.5 9 23 ± 1.5 17 ± 0.6 3 54 65 30 76 23 23 Zn Table 2. Contents of water extractable elements at 1:200 litter to water extraction ratio in raw, ground, and granulated poultry litters where several granulated poultry litters had urea, urea and dicyandiamide (DCD), or hydrolyzed feathermeal added as an additional N source 1 a–d Values followed by different letters in the same column are significantly different at P < 0.05. Total N and P data from Toor et al. [24]. 2 Note: Raw litter no. 1 was heated to produce heated litter no. 1. Source no. 1 Raw litter no. 1 Ground litter no. 1 Heated litter no. 12 Granulated litter no. Granulated litter no. Granulated litter no. Source no. 2 Ground litter no. 2 Granulated litter no. Poultry litter treatment Table 1. Total contents of N, P, and trace elements in raw, ground, and granulated poultry litters where several granulated poultry litters had urea, urea and dicyandiamide (DCD), or hydrolyzed feathermeal added as an additional N source1 TOOR ET AL.: WATER EXTRACTABLE TRACE ELEMENTS 353 JAPR: Research Report 5.5 ± 0.3 4.6 ± 0.2 0.6 2.9 ± 0.1 3.4 ± 0.1 0.3 10.0 ± 0.2 6.4 ± 1.7 2.8 37.6 ± 0.9 32.6 ± 1.3 2.5 5.2 6.3 7.9 9.2 3.4 3.4 4.4 3.5 1.7 2.6 1.4 0.2 19.0 ± 22.2 ± 9.6 ± 18.8 ± 13.7 ± 16.1 ± 4.8 3.1 1.3 1.1 0.5 0.7 2.1 54.8 ± 24.8 51.1 ± 25.7 7.3 29.0 ± 0.9 29.3 ± 0.9 2.1 2 with feathermeal 1 1 with urea 1 with urea and DCD Source no. 1 Raw litter no. 1 Ground litter no. 1 Heated litter no. 1 Granulated litter no. Granulated litter no. Granulated litter no. LSD (0.05) Source no. 2 Ground litter no. 2 Granulated litter no. LSD (0.05) % of total 40.8 ± 40.7 ± 14.5 ± 41.1 ± 29.4 ± 32.9 ± 3.0 72.1 ± 9.0 77.3 ± 5.7 83.7 ± 6.6 78.3 ± 10.7 82.1 ± 6.0 82.0 ± 5.8 13.5 69.9 ± 13.5 63.5 ± 5.8 54.9 ± 10.8 60.3 ± 3.1 61.2 ± 15.0 62.7 ± 1.6 17.3 28.5 ± 29.9 ± 35.5 ± 33.9 ± 27.9 ± 28.7 ± 4.3 4.8 2.0 2.1 0.7 1.4 1.0 82.0 ± 1.2 89.1 ± 2.2 4.0 1.7 0.7 0.9 0.3 0.1 0.5 8.8 ± 10.2 ± 4.9 ± 12.2 ± 4.4 ± 4.7 ± 1.5 ± 0.7 ± 0.5 ± 0.1 ± 0.4 ± 0.1 ± 0.1 0.7 Zn Mn Fe Cu B As P Poultry litter treatment raw poultry litter was heated at 180°C for 2 h (heated litter no. 1) at our laboratory. A second poultry litter source was obtained from Organic-Gro Inc. [20]. At this facility, ground poultry litter was passed through a 2.5mm vibrating screen and then mixed with hydrolyzed feathermeal before granulation. Two treatments resulted from this litter source: 1) ground poultry litter (ground litter no. 2); and 2) granulated mixture of poultry litter and hydrolyzed feathermeal (granulated litter no. 2 with feathermeal). This facility dried granulates to less than 8% moisture to avoid composting during storage and produces a commercially available product (see http://www.organic-gro.com/40824.shtml). Poultry Litter Extraction and Analyses Total As, B, Cu, Fe, Mn, P, and Zn in the raw and granulated poultry litters were determined, in triplicate, using concentrated HNO3 and H2O2 digestion followed by inductively coupled plasma-optical emission spectroscopy (ICPOES) analysis [21]. Water extractable (WE) As, B, Cu, Fe, Mn, P, and Zn were measured by extracting poultry litters, in triplicate, at poultry litter (dry weight equivalent) to deionized water ratios of 1:10, 1:50, 1:100, 1:200, and 1:250. For example, the 1:10 ratio had 20 g of dry weight equivalent of poultry litter mixed with 200 mL of water (including ambient moisture in the poultry litter), and this volume of water (200 mL) was used in all extracts. The mixture was shaken for 2 h in a reciprocating shaker followed by centrifugation at 2,900 rpm for 20 min before filtration through a 0.45-m nylon membrane. The filtered aliquot from the various ratios was analyzed for WE As, B, Cu, Fe, Mn, P, and Zn by ICP-OES. Statistical Analyses Descriptive statistics and 1-way ANOVA with means separation using the LSD were performed by Genstat 4.2, 5th edition [22] to calculate means, SD, and to test for significant effects of litter sources and extraction ratios on the trace elements. Statistical comparisons were determined at P < 0.05. Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 Table 3. Percentage of water extractable elements at 1:200 litter to water extraction ratio in raw, ground, and granulated poultry litters where several granulated poultry litters had urea, urea and dicyandiamide (DCD), or hydrolyzed feathermeal added as an additional N source 354 TOOR ET AL.: WATER EXTRACTABLE TRACE ELEMENTS 355 Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 Figure 1. Concentrations of trace elements in aliquots from the water extractions at the various poultry litter to water extraction ratios. The regression line represents the overall trend for all litters. DCD = dicyandiamide. RESULTS AND DISCUSSION Total Trace Element Contents in Poultry Litters Total contents of all trace elements were generally lower in the granulated products than ground litter (Table 1), where granulation of poultry litter and addition of additives (i.e., urea, DCD or hydrolyzed feathermeal) significantly reduced contents of As, B, Cu, Mn, and Zn compared with raw or ground litter with in each poultry litter source (i.e., litter no. 1 or 2). This decrease in trace elements content is attributed to the dilution of litter with additives in the granulated products, not because of the granulation process. As a comparison, total P contents were also significantly lower in the granulated products, whereas total N was significantly increased in the granulated products compared with ground litter because of the presence of N in the urea and hydrolyzed feathermeal. Trace element contents differed in poultry litters obtained from 2 sources, likely from differences in poultry diets. For example, poultry litter no. 1 had greater contents of 356 Effect of Extraction Ratios on Water Extractable Trace Element Concentrations and Contents in Poultry Litters Concentrations of soluble As, B, Cu, Fe, Mn, and Zn in the water extracts decreased with an increase in extraction ratio from 1:10 to 1:250 (Figure 1). The concentration of As in the water extracts from the various poultry litters was 1.05 to 2.35 mg/L at 1:10, which decreased to 0.05 to 0.12 mg/L at 1:250 extraction ratio. Moore et al. [8] reported initial soluble As concentrations of >0.2 mg/L in runoff from a soil amended with poultry litter at 9 mg/ha, and it appears that concentrations of As in runoff waters from Moore et al. [8] were in the range we observed at the 1:100 extraction ratio (0.13 to 0.29 mg/L). Moore et al. [8] also reported soluble Cu levels in runoff waters up to 1 mg/L, which is approaching the US EPA drinking water maximum contaminant level of 1.3 mg/L. In our litters, we observed concentrations of Cu from 0.92 to 2.35 mg/L in the water extract at the 1:100 extraction ratio (Figure 1). The similarity of these soluble As and Cu concentrations in our water extracts to runoff concentrations of Moore et al. [8] indicates that a quick water extraction of poultry litter in the laboratory may help to assess the solubility and runoff potential of trace elements from land applied poultry litter. This also supports our previous observation [24] that litter to water extraction ratio from 1:100 to 1:200 may be the best indicator to assess the potential release of P and could also be used for risk assessment of trace element loss to water. Although trace element concentrations (mg/ L) in the water extracts decreased with an increase in extraction ratios from 1:10 to 1:250, the contents (mg/kg) of WE As, B, Cu, Fe, Mn, and Zn increased with an increase in extraction ratio from 1:10 to 1:200 (Figure 2). Contents of WE As and Cu were not significantly different between 1:100 and 1:200 extraction ratios, whereas WE B, Fe, Mn, and Zn were significantly higher at 1:200 (5 to 13%) than 1:100 extraction ratio. Based on these limited observations, we suggest using 1:200 extraction ratio to extract most of the WE trace elements in poultry litters. It is important to note, however, that concentrations of all trace elements were lower at the 1:200 extraction ratio than 1:100, and the concentrations of several trace elements (e.g., Cd, Cr, and Mo) were below the detection limits of ICP-OES beyond the 1:10 extraction ratio (data not shown). For example, at the 1:10 extraction ratio, the concentrations of Cd, Cr, and Mo were <0.10, <0.19, and <0.15 mg/L, respectively, for all litters. Therefore, if the objective of the study is to determine the concentrations of Cd, Cr, and Mo in litters, researchers should use lower extraction ratio (preferable 1:10) to obtain measurable amounts. The following section focuses on the contents of WE As, B, Cu, Fe, Mn, and Zn at the 1:200 extraction ratio because this extraction ratio extracted most of the soluble forms of these trace elements. Water Extractable Trace Elements Contents in Poultry Litters at 1:200 Extraction Ratio Contents of WE As in litters and granulated products ranged from 10 to 30 mg/kg (Table 2). Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 As, Cu, Mn, and Zn than poultry litter no. 2 (Table 1). Among these 6 trace elements discussed, As contents were least (20 to 44 mg/kg) followed by B (54 to 122 mg/kg) then Cu, Fe, Mn, and Zn, which were generally similar in magnitude. However, the contents of Co (<0.6 mg/kg), Cr (0.5 to 2.2 mg/kg), and Mo (0.7 to 1.5 mg/kg) were least among all trace elements determined via ICP-OES (data not reported). The maximum allowed limits of As for land application in biosolids is 41 mg/kg [1]; therefore, raw or ground poultry litter no. 1 had As contents (41 to 44 mg/kg) at or slightly more than the biosolids limits. However, the granulated products from poultry litter no. 1 that included additives (i.e., urea and urea plus DCD) had As contents that were less (32 to 33 mg/kg) than the biosolids limits for As content (Table 1). Similarly, the poultry litters from the other source (no. 2) had As contents approximately half of the biosolids limits. The contents of Cu and Zn in litters and granulated products (<647 mg/kg) were well below the threshold limits for land application of biosolids (1,500 and 2,800 mg/kg, respectively) [1]; therefore in the short-term, litter application may not affect the soil trace element contents to a great extent. However, several previous studies have shown that long-term application of poultry litters to soil can elevate trace element contents above soils that do not receive manure applications [5, 23]. JAPR: Research Report TOOR ET AL.: WATER EXTRACTABLE TRACE ELEMENTS Contents of WE B, Fe, Mn, and Zn were less than 123 mg/kg for all poultry litters, whereas WE Cu ranged from 263 mg/kg in the ground litter no. 1 to 135 to 243 mg/kg in the granulated litters (no. 1). In contrast, the contents of water extractable P were significantly greater in the heated litter (8,029 mg/kg) than other litters whether granulated or not and significantly lower in the granulated products that contained urea, urea plus DCD, or hydrolyzed feathermeal (4,542 to 4,934 mg/kg) than raw and ground litters (5,291 to 7,043 mg/kg). Among trace elements, As, B, and Cu exhibited greater water solubility (15 to 89%), whereas Mn and Zn were less water soluble (3 to 12%) in litters (Table 3). In comparison, water extractability of P ranged from 28 to 36% at 1:200 for all litters, with nonsignificant differences between granulated litters that had urea, urea plus DCD, or hydrolyzed feathermeal and ground litters with in each litter source (no. 1 or 2). Likewise, the percentages of WE As were not significantly different for the ground and granulated litters from both sources, whereas WE Cu and Zn were significantly lower in the granulated products with urea, urea plus DCD, or hydrolyzed feathermeal compared with ground litter in each source. At the 1:200 extraction ratio, 51 to 70% of As was WE, which indicates that this element will be readily soluble when poultry litter is land applied. Organo-arsenic compounds such as roxarsane or p-arsanilic acid, when added to feed, are apparently excreted by birds in relatively unchanged chemical forms. Jackson et al. [10] fractionated WE As in poultry litters and observed roxarsane and p-arsanilic acid as major As contributors, along with their metabolites (arsenite, arsenate, mono- and di-methyl arsinate, and unknowns). However, once organo–arsenic compounds present in poultry litter are applied to soil, the organic forms break down into metabolites that vary in mobility and toxicity [25, 26]. For example, the soluble inorganic arsenicals are known to be more toxic than the organic forms to the animal health and the arsenites (AsIII) are more soluble, mobile, and toxic than arsenates (AsV), which are strongly adsorbed by soil constituents [27]. Contents and percentages of WE Cu were greater than WE Zn for all litters (Tables 2 and 3). Copper and Zn are added to animal feeds as a sulfate salt or oxide and presumably occur in the litter in ionic form. However, both these elements can form stable complexes with the organic matrix of litters; as a result, their mobility can be affected when land applied [11, 28]. The percentages of WE Cu and Zn were significantly reduced by 1 to 6% (Zn) and 5 to 8% (Cu) in the granulated litters that had urea, urea plus DCD, and hydrolyzed feathermeal when compared with ground litter for each source. This may be due to the transformation of Cu and Zn to less soluble forms during litter granulation that involved heating and drying at higher temperatures. The observation that the heated litter no. 1 had significantly reduced WE Cu and Zn contents also supports the transformation from soluble to less soluble forms during drying at higher temperatures. Among polyvalent cations, water solubility was relatively low for Fe (6 to 22%), Mn (3 to 9%), and Zn (4 to 12%), indicating that these Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 Figure 2. Water extractable elements expressed as percent of water extractable (WE) elements at 1:250 extraction ratio for poultry litters. Values are means for 8 poultry litters for each element at each extraction ratio. Standard deviation is shown by vertical lines. a–d Letters followed by the different letters for each element are significantly different at P < 0.05. 357 358 JAPR: Research Report elements are present in adsorbed forms and are not easily released by water extraction (Table 3). Also, the lower water extractability of Fe, Mn, and Zn compared with other elements suggest that these may be major cations responsible for adsorbing anions such as As and P, which are more soluble in the water extracts. Implications of Trace Element Loading in Intensive Poultry Production Regions Figure 3. Estimated total and water extractable trace elements loading from poultry litter application at the 100 kg of total P/ha. Standard deviation is shown by vertical lines. a–cColumns within each element having different letters are significantly different at P < 0.05. NS = nonsignificant within each litter source (i.e., no. 1 or 2). DCD = dicyandiamide. 1.2 and 3.1 kg/ha, respectively, which is approximately 2-fold lower for Cu and similar for Zn than our poultry litters. Nicholson et al. [2] calculated that at an application level supplying 250 kg of N/ha, poultry manures would add 1.1 and 0.5 kg/ha of Cu and Zn, respectively. It is important to be aware that trace element additions to soils may vary from our calculated values and among different studies because of the variability of these elements in poultry litters or other manure types and due to the different land application practices, such as total N or P based, used on the farms or regions. Importantly, the commercial nutritionists need to be educated about the risks to soil and water quality so that they can safely modify nutrient margins not only for environmental purposes but also for sustaining commercial operations. Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 Poultry litter is a valuable source of organic matter, major plant nutrients, and some trace elements; however, excessive addition of these elements in poultry diets results in greater amount in litters and raises concerns about excessive element loading to soils. For example, Nicholson et al. [2] reported that each year animal manure applications contribute 1,821 mg of Cu and 5,247 mg of Zn to the England and Wales soils, which corresponds to 25 to 40% of the total annual inputs of these elements to soils. We calculated the typical amounts of trace elements added to soil if raw and granulated poultry litter products are applied at rates supplying 100 kg total P/ha per yr (∼90 lb of P/ac), in accordance with the maximum allowable P inputs under P-based management practices in the Eucha-Spavinaw Basin in Northwest Arkansas [29]. Although a greater mass of granulated products that contained urea (5,650 kg/ha), urea plus DCD (5,952 kg/ha), or hydrolyzed feathermeal (6,452 kg/ha) would be land applied than ground litter no. 1 (4,237 kg/ ha) or ground litter no. 2 (5,464 kg/ha) due to the lower total P content of granulated products, generally the total addition of As, Cu, and Zn to soil would be similar from ground and granulated litters (Figure 3). For example, raw or ground litters and granulated products would add 0.13 to 0.19 kg of total As/ha, 1.9 to 2.7 kg of total Cu/ha, and 2.3 to 2.9 kg total Zn/ha to soil, if litter is applied at 100 kg of total P/ha. The total addition of As from our litters with a 1-time application is below the US EPA annual application limit of 2 kg/ha [1]; however, the greater solubility of As in litters (WE-As: 0.07 to 0.13 kg/ha; 51 to 70% of total) may result in greater addition of WE As to soils, as has been also reported by Christen [30]. McBride and Spiers [31] calculated that if dairy manures are applied at 150 kg P/ha, the annual loadings of Cu and Zn would be about TOOR ET AL.: WATER EXTRACTABLE TRACE ELEMENTS to soil, dairy manure application would add 70fold greater Zn and 2,000-fold greater Cu than from commercial fertilizers. Clearly, to reduce the concerns of trace elements accumulations in soils, the best management practices should aim to decrease the output of trace elements in animal manures. This may involve dietary modifications to match trace element contents in feeds with animal requirements. Research is evidently needed to better understand utilization of trace elements by animals so that the excessive addition of trace elements in diets could be reduced. For example, Mohanna and Nys [32] reported that reduction in dietary Zn contents in poultry diets from 190 to 60 mg/kg decreased Zn excretion in poultry litters by 75%, and this reduction did not adversely affect enzyme activity or immune response of the chicks. The knowledge gained by the research on the trace element utilization by animals would help to optimally balance rations so that the amounts of trace elements in diets does not result in excessive levels in manures, which would reduce the future build-up of trace elements in soils when manures are land applied. CONCLUSIONS AND APPLICATIONS 1. Addition of urea, urea plus DCD, and hydrolyzed feathermeal to poultry litter during litter granulation diluted total contents of As, Cu, and Zn by 10 to 25% compared with raw and ground litters, without affecting water extractable contents. 2. An increase in litter to water extraction ratio increased water extractable contents of all trace elements. It appears that 1:200 extraction ratio offers the best option to extract most of the water extractable trace elements in poultry litters. However, at the 1:200 extraction ratio, several trace elements concentrations were below the detection limits of ICP-OES, for which a lower extraction ratio (1:10) needs to be used. 3. Addition of As, Cu, and Zn to soils with a 1-time application of poultry litter, whether granulated or not, would be much lower than the US EPA annual application limits of trace elements for biosolids; however, repeated application of litter will likely result in soil loading of trace elements above environmental thresholds. REFERENCES AND NOTES 1. US EPA. 1993. Part 503 - Standards for the use or disposal of sewage sludge. Fed. Regist. 59:9387–9404. 2. Nicholson, F. A., B. J. Chambers, J. R. Williams, and R. J. Williams. 1999. Heavy metal contents of livestock feeds and animal manures in England and Wales. Bioresour. Technol. 70:23–31. 3. Gascho, G. J., and R. K. Hubbard. 2006. Long-term impact of broiler litter on chemical properties of a Coastal Plain soil. J. Soil Water Conserv. 61:65–74. 4. Gupta, G., and S. Charles. 1999. Trace elements in soils fertilized with poultry litter. Poult. Sci. 78:1695–1698. 5. Han, F. X., W. L. Kingery, H. M. Selim, and P. D. Gerard. 2000. Accumulation of heavy metals in a long-term poultry wasteamended soil. Soil Sci. 165:260–268. 6. Li, Z. B., and L. M. Shuman. 1997. Mobility of Zn, Cd and Pb in soils as affected by poultry litter extract. 1. Leaching in soil columns. Environ. Pollut. 95:219–226. Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 In areas where animal manures have been applied for many years and where manure applications are expected to continue, it is likely that trace element accumulation rates (particularly Cu and Zn) will be at their greatest. However, the loadings of Cu and Zn (∼2 to 3 kg/ha) to soil from 1 application of our poultry litters and granulated products are well below the USEPA environmental thresholds of 75 kg of Cu/ha and 140 kg of Zn/ha for biosolids [1]. In addition, most of the Cu and Zn in poultry litters were present in the complexed forms (i.e., not water extractable); therefore, one application would likely result in inconsequential effects on soil Cu and Zn contents. Evidently, the greater concern with the long-term land application of litters lies with Cu and Zn, whereas the other trace elements (Pb, Hg, Cd, etc.) are rarely found in elevated amounts in poultry litters. Han et al. [5] and Kingery et al. [23] reported that the long-term land application of poultry litter may result in substantial cumulative loadings of these elements as evidenced by increased contents of Cu and Zn in soils and leachates. Similarly, McBride and Spiers [31] reported that a given rate of P applied 359 JAPR: Research Report 360 7. Pirani, A. L., K. R. Brye, T. C. Daniel, B. E. Haggard, E. E. Gbur, and J. D. Mattice. 2006. Soluble metal leaching from a poultry litter-amended Udult under pasture vegetation. Vadose Z. J. 5:1017–1034. 24. Toor, G. S., B. E. Haggard, M. S. Reiter, T. C. Daniel, and A. M. Donoghue. 2007. Phosphorus solubility in poultry litters and granulates: Influence of litter treatments and extraction ratios. Trans. ASAE. 50:533–542. 8. Moore, P. A., Jr., T. C. Daniel, J. T. Gilmour, B. R. Shreve, D. R. Edwards, and B. H. Wood. 1998. Decreasing metal runoff from poultry litter with aluminum sulfate. J. Environ. Qual. 27:92–99. 25. Smith, E., R. Naidu, and A. M. Alston. 1998. Arsenic in the soil environment: A review. Adv. Agron. 64:149–195. 9. van der Watt, H. V. H., M. E. Sumner, and M. L. Cabrera. 1994. Bioavailability of copper, manganese, and zinc in poultry litter. J. Environ. Qual. 23:43–49. 10. Jackson, B. P., P. M. Bertsch, M. L. Cabrera, J. J. Camberato, J. C. Seaman, and C. W. Wood. 2003. Trace element speciation in poultry litter. J. Environ. Qual. 32:535–540. 11. Bolan, N. S., D. C. Adriano, and S. Mahimairaja. 2004. Distribution and bioavailability of trace elements in livestock and poultry manure by-products. Crit. Rev. Environ. Sci. Technol. 34:291–338. 12. Miller, R. E., X. Lei, and D. E. Ullrey. 1991. Trace elements in animal nutrition. Pages 593–662 in Micronutrients in Agriculture. 2nd ed. J. J. Mortvedt, ed. Soil Sci. Soc. Am., Madison, WI. 14. New Holland Equipment, New Holland, PA. 15. Mosaic Co., Plymouth, MN. 16. Agrotain Int., LLC, Collierville, TN. 17. 12D54L Pin Mixer, Mars Mineral Inc., Mars, PA. 18. 101 and 1015 Series Volumetric Screw Feeders, Acrison Inc., Moonachie, NJ. 19. Amberger, A. 1989. Research on dicyandiamide as a nitrification inhibitor and future outlook. Commun. Soil Sci. Plant Anal. 20:1933–1955. 20. Organic-Gro Inc., Framingham, MA. 21. Zarcinas, B. A., B. Cartwright, and L. R. Spouncer. 1987. Nitric acid digestion and multi-element analysis of plant material by Inductively Coupled Argon Plasma Spectroscopy. Commun. Soil Sci. Plant Anal. 18:131–146. 22. Genstat, 5th Ed., Lawes Agricultural Trust, Rothamsted, UK. 23. Kingery, W. L., C. W. Wood, D. P. Delaney, J. C. Williams, and G. L. Mullins. 1994. Impact of long-term application of broiler litter on environmentally related soil properties. J. Environ. Qual. 23:139–147. 27. Maeda, S. 1994. Biotransformation of arsenic in the freshwater environment. Pages 155–187 in J. O. Nriagu, ed. Arsenic in the Environment. Part I, Cycling and Characterization. Wiley-Interscience, New York, NY. 28. Adriano, D. L. 2001. Trace elements in terrestrial environments: Biogeochemistry, bioavailability and risks of metals. Springer, New York, NY. 29. DeLaune, P. B., B. E. Haggard, T. C. Daniel, I. Chaubey, and M. J. Cochran. 2006. The Eucha/Spavinaw phosphorus index: A court mandated index for litter management. J. Soil Water Conserv. 61:96–105. 30. Christen, K. 2001. Chickens, manure, and arsenic. Environ. Sci. Technol. 35:184A–185A. 31. McBride, M. B., and G. Spiers. 2001. Trace element content of selected fertilizers and dairy manures as determined by ICP-MS. Commun. Soil Sci. Plant Anal. 32:139–156. 32. Mohanna, C., and Y. Nys. 1999. Effect of dietary zinc content and sources on the growth, body zinc deposition and retention, zinc excretion and immune response in chickens. Br. Poult. Sci. 40:109– 114. Acknowledgments This project was made possible by Organic-Gro Inc. and Mars Mineral Inc.; without the cooperation of these companies, the granulated products would not have been evaluated in this study. Funding for this project was provided by the US Poultry and Egg Association Research Support Program, the US Department of Agriculture – Agricultural Research Service, and the University of Arkansas—Division of Agriculture. We would like to thank Stephanie Williamson for her dedicated work on this project during poultry litter extractions and laboratory analyses. This project benefited from valuable consultation with Daniel Pote and Tommy Daniel, and this manuscript benefited from reviews by several anonymous technical reviewers. Downloaded from http://japr.oxfordjournals.org/ by guest on July 6, 2015 13. Kelley, T. R., O. C. Pancorbo, W. C. Merka, S. A. Thompson, M. L. Cabrera, and H. M. Barnhart. 1996. Elemental concentrations of stored whole and fractionated broiler litter. J. Appl. Poult. Res. 5:276–281. 26. Bednar, A. J., J. R. Garbarino, I. Ferrer, D. W. Rutherford, R. L. Wershaw, J. F. Ranville, and T. R. Wildeman. 2003. Photodegradation of roxarsone in poultry litter leachates. Sci. Total Environ. 302:237–245.
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