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«A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Crop, Soil, and Environmental Sciences ...»

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Economic growth equated to a population explosion with a 2007 population exceeding 421,000 (15% of Arkansas population) that produces over 75 000 Mg of biosolids (BS) per year (Northwest Arkansas Conservation Authority, 2003; USA Census Bureau, 2007). Biosolids from the 5 major municipalities in NWA are currently land filled as land application is not practiced due to the perceived risk of P loss and potential liability (DeLaune et al., 2006).

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The USEPA (2000) identified N and P from agricultural non-point sources as the major source of surface water contamination in the United States. Excess N and P additions to waterways accelerate the natural eutrophication phenomenon resulting in noxious aquatic algae's weed growth (Levine and Schindler, 1989; Daniel et. al., 1994).

Although N and P both influence algae growth, waterways are generally P deficient (Thomann and Mueller, 1987). Therefore, the main focus for reducing accelerated eutrophication in most freshwater bodies is to minimize surface water P inputs (Daniel et.

al., 1994).

Confined animal feeding operations were cited as significant sources for P loading into waterways (Sharpley et al., 1994). Historically, CAFOs applied manures to soils close to the production unit, which over time increased soil-P concentrations above agronomic needs (Slaton et al., 2004). Slaton and coworkers (2004) projected that nutrient inputs from the poultry and cattle industries increased soil test P (STP) concentrations by 2.5 mg P kg soil"1 per year on cool- and warm-season grasses in NWA.

According to their calculations, an excess of 12.5 kg manure P ha" yr" was added to the fescue (Festuca arundinacea Schreb.) and bermudagrass {Cynodon dactylon) pastures above crop removal. As of 2006, 78% of soils submitted to the Arkansas Soil Testing Laboratory from NWA tested above the optimum (50 mg P kg"1) agronomic P fertility level with 39% of the soils containing P concentrations in excess of 150 mg P kg"1 (DeLong et. al., 2007; Espinoza et. al., 2007).

Past research indicated that runoff dissolved reactive P (DRP) concentrations increased linearly as STP increased until a P threshold was reached (Daniel et al., 1994;

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STP concentration, soil extract and runoff water concentrations rapidly increased due to soil adsorption site saturation (Kleinman et al., 2000; McDowell and Sharpley, 2001).

Soils with Mehlich-3 P concentrations up to 553 mg P kg"1 supported the P threshold theory in a study by McDowell and Sharpley (2001). Soils generally had a linear response between water and weak salt extractable P and Mehlich-3 STP until a breakpoint of approximately 190 mg P kg"1 was reached. After this point, the relationship showed a non-linear rapid increase in runoff DRP as STP increased. Therefore, P additions to saturated soil may rapidly increase runoff water DRP concentrations and increase eutrophication.

Ultimately, the key to reducing DRP concentrations in runoff is to reduce P loss, which is highest after the initial rainfall event following application. Edwards and Daniel (1994) showed that the first rainfall event following fertilizer application had the greatest environmental risk due to highest P and N losses. In their study, runoff nutrient concentrations reached background runoff water concentrations by the second rainfall event; therefore, keeping nutrients in insoluble forms by encapsulating them into a physically water resistant compound may decrease overall nutrient loss.

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Soil-P solubility fluxes as pH and buffering capacity change due to varying concentrations of clay, Fe and Al oxides, carbonates, and organic matter (Lindsay, 1979).

Phosphorus is rendered less available by reactions with Fe and Al at low soil pH (6.5 pH) and Ca reduces P availability due to secondary mineral formation at a higher (6.5 pH) soil pH (Lindsay, 1979). Calcium, an amendment in poultry feed, may change acidic

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1992; Kingery et al., 1994; Sharpley and Smith, 1995). Long-term additions of PL containing Ca could potentially influence the partitioning of soil P, shifting the dominant inorganic P forms from Al- and Fe-bound fractions to less water soluble Ca-bound forms (Sharpley and Smith, 1995; Wang et al, 1995; Sharpley et al, 2004). Although P associations are normally pH dependent, Delgado and Torrent (2000) found considerable Ca phosphate minerals in both calcareous and acid limed soils managed with long-term P fertilization. Inversely, Pierzynski and coworkers (1990) found Al-phosphate minerals were the predominant soil-P fraction regardless of soil pH on heavily fertilized soils. Soil P fractionation techniques can be employed to estimate P cationic associations for understanding of overall environmental and plant availability (Kuo, 1996).

Torbert and coworkers (2002) found evidence of pH impacting DRP in runoff water concentrations during a rainfall simulation study. In their study, lower runoff DRP concentrations were found in calcareous soils compared to acidic soils having comparable STP concentrations. They attributed lower DRP concentrations in calcareous soils to relatively insoluble Ca-bound P mineral formation. Long term PL amendments may ultimately impact soil chemistry and change a soil's overall P solubility scheme.





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Poultry litter and BS are proven fertilizer sources and possess dramatic restorative qualities when applied to soils (Reynolds, 1926; Hinesly et. al., 1972; Shortall and Liebhardt, 1975; Bitzer and Sims, 1988; Sistani et al., 1988; Miller et al., 1990; Miller et al., 1991; Edwards and Daniel, 1992; Cooperband et al, 2002; Gilmour et. al, 2003;

Brye et al., 2005; Mitchell and Tu, 2005). However, unaltered PL and BS fertilizers are

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have odor and a negative stigma (McMullen et. al., 2005; Mitchell and Tu, 2005). The low nutrient concentration and bulk density not only make the materials less manageable than commercial fertilizers, but also increase their hauling cost per kg nutrient, thus limiting their use to within 40 km from the source (Bosch and Napit, 1992; Govindasamy and Cochran, 1995). Based on N, P, and K concentrations and the corresponding fertilizer value, Armstrong and coworkers (2007) found that PL and BS were worth $63.65 and $67.02 per 1000 kg, respectively.

Although low compared to commercially available inorganic fertilizers, PL and BS both contain appreciable concentrations of nutrients. On average, PL contains approximately 35 to 40 g total N kg litter"1, with most N in the organic form (-70%) and the remainder (30%) residing in inorganic fractions mainly as NH4-N (Sims, 1986; Sims, 1987; Westerman et al., 1987; Edwards and Daniel, 1992; Malone, 1992). Negligible NO3-N concentrations were found in PL unless it was stored in an aerobic and moist environment (Sims and Wolf, 1994). Similar to PL, USEPA (1995) reported mean BS values of 39 g total N kg"1 with 18% of total N present as inorganic N. Nearly all BS inorganic N was present as NH4-N, with negligible NO3-N concentrations, in several studies (Gilmour and Skinner, 1999; Gilmour et. al., 2003; Cogger et. al, 2004).

High concentrations of organic N in PL offer slow N release characteristics over a growing season following application. Organic PL fractions are composed of labile and complex organic N forms as discussed in a comprehensive review by Sims and Wolf (1994). Labile organic N forms are largely present as uric acid and urea and are rapidly hydrolyzed by uricase and urease enzymes to urea and NH3-N, respectively (Sims and

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hours if suitable moisture and temperature are present (Lacey et al., 1981). However, complex organic N forms take longer than labile N complexes to mineralize as discussed by Hadas and coworkers (1983). In their study, a two phase mineralization scheme was proposed when PL was applied to soils in ground or pelleted forms. Initially, 34 to 42% of total N was mineralized and a slower release phase was observed over the next 13 wk with up to 50% of total N being mineralized. Similar results were reported by Bitzer and Sims (1988) whom indicated two distinct mineralization phases, with the initial phase being defined as N mineralization from 0 to 14 d and the second, nonlabile phase being measured from 14 to 140 d. Gale and Gilmour (1986) proposed three main phases in PL mineralization. Rapid, intermediate, and slow mineralization phases were measured via C evolution after PL was added to soil. Overall, Pratt and coworkers (1973) proposed that 90% of the PL organic fraction is mineralized over a growing season while Bitzer and Sims (1988) estimated approximately 66% organic N mineralization using upland crop and incubation studies. However, overall N use by plants varies greatly by production system as Golden and coworkers (2006) only reported 14% of total PL N assimilation in flood irrigated rice systems.

Biosolids were also shown to have significant N mineralization when applied to soil in various field and incubation trials. For nutrient planning purposes, the USEPA (1995) recommended 20 to 30% total-N availability the first year following application with 10 to 15% becoming plant available the second year. However, other studies shown slightly higher total N availability ranging from 37 to 40% in the first year following application (Gilmour et. al., 2003; Gilmour and Skinner, 1999).

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increase STP when applied to soils. Allen and Mallarino (2006) found a positive nonlinear correlation between Mehlich-3 STP and cumulative P applied. Sims and coworkers (1991) found that PL applications for two years to Delaware soils significantly increased STP concentrations for various crop rotations. Generally, 4 to 5 mg P kg soil'1 fertilization results in a 1 mg P kg"1 increase in STP for Arkansas silt loam soils (DeLaune and Moore, 2001; Slaton et. al., 2003).

Organic fertilizer sources not only offer slow nutrient release over a growing season, but they may also be less detrimental to water quality following application compared to inorganic sources. Research by Edwards and Daniel (1993,1994) found that PL generally produced lower inorganic N, total Kjeldahl N, DRP, and total P runoff concentrations than inorganic fertilizer sources applied at comparable rates. However, PL treatments did have higher chemical O2 demands and more total suspended solids in runoff so total environmental risks were not abated. Gaudreau and coworkers (2002) showed similar results with 44% less DRP in runoff following PL applications compared to inorganic P fertilizers. Similar to PL, McLeod and Hegg (1984) found that municipal BS produced lower N concentrations in runoff than either PL or inorganic fertilizer on tall fescue pastures.

FRESH POULTRY LITTER AND BIOSOLIDS SOURCE TRANSFORMATION

Agglomeration is the process of combining small particles into a larger mass for dust reduction, ease of handling, flowability, solubility control, and homogeneity (Browning, 1967). Specifically for PL and BS fertilizers, agitated granulation in combination with sintering may be useful for manufacturing innovative fertilizer sources.

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through interaction with a liquid phase to form seed nuclei. Particle growth takes place on these nuclei due to cohesion promoted by binding agents and/or layering resulting in a finished granule of desired size (Browning, 1967; Adetayo et. al., 1993). Pin mixers add aggressive agitation that aids in granule formation when using irregular and traditionally difficult substances to granulate (Adetayo et. al, 1993; Johnson and Sturgess, 2003).

Sintering, a heat reaction bonding that forms agglomerates through partial fusion of the material itself or with a binder, offers additional granule strength as moisture is removed following the agglomeration step of the process, effectively making stable molecules (Browning, 1967).

Past research indicated that cylindrical pelletizing of PL via extrusion technology (forcing material though metal dies in conjunction with a binding agent) increased PL bulk density, offered uniformity regarding size and shape, and allowed for fortification with nutrients (Hamilton and Sims, 1995; McMullen et. al, 2005). A study by McMullen and coworkers (2005) found that pelletization increased PL fertilizer bulk density four fold and made physically sound fertilizers. However, pellet moisture content significantly affected durability and must be considered when designing dry down procedures, hauling, and storage of fertilizer products (McMullen et. al., 2005). Other research found similar results indicating that bulk density of fresh organic materials were increased from 40-200 kg m"3 to 600-800 kg m"3 using agglomeration procedures resulting in materials that are easier to handle, transport, and store (Mani et. al., 2003; Obernberger and Thenk, 2004).

Grinding and drying (exposure to high heat) PL and BS are necessary for the

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Kaliyan and Morey, 2006). However, processing may change N release characteristics compared to fresh ingredients but results vary by study and material. For instance, Hadas and coworkers (1983) showed more inorganic N release from pelletized PL compared to fresh PL and linked the mineralization increase to more surface area exposure to microbes due to the grinding process. Similar results were confirmed by Cabrera and coworkers (1994) during an incubation study. However, Cabrera and coworkers (1993) also demonstrated that N volatilization and N mineralization rates were similar in both fresh and pelletized PL sources in a separate incubation study. Golden and coworkers (2006) reported no statistical differences between rice plant N assimilation and overall grain yield when rice was fertilized with fresh or pelletized PL.

Regarding BS, Cogger and coworkers (2004) found differing N mineralization rates depending on the wastewater treatment plant process. In their study, heat-dried BS had more plant-available N during the first year after application compared to air-dried or de-watered BS. Smith and Durhman (2002) found similar results and postulated that NH4-N found in the BS and lost during heating had little impact on plant-available N concentrations. In field and incubation studies, Gilmour and coworkers (2003) and Cogger and coworkers (1999) did not find any statistical differences in plant-available N between not-dried versus heat-dried BS.



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