Phosphorus speciation in broiler litter and turkey manure produced from modified diets

Modifying poultry diets by reducing mineral P supplementation and/or adding phytase may change the chemical composition of P in manures and affect the mobility of P in manure-amended soils. We studied the speciation of P in manures produced by broiler chickens and turkeys from either normal diets, or diets with reduced amounts of non-phytate phosphorus (NPP) and/or phytase, using a combination of chemical fractionation and synchrotron X-ray absorption near edge structure (XANES) spectroscopy. All broiler litters were rich in dicalcium phosphate (65-76%), followed by aqueous phosphate (13-18%), and phytic acid (7-20%); however, no hydroxylapatite was observed. Similarly, normal turkey manure had 77% of P as dicalcium phosphate and had no hydroxylapatite, while turkey manure from diets that had reduced NPP and phytase contained equal proportions of dicalcium phosphate (33-45%) and hydroxylapatite (35-39%). This is attributed to the higher total Ca to P ratio (>2) in modified turkey manures that resulted in transformation of more soluble (dicalcium phosphate) to less soluble P compounds (hydroxylapatite). Chemical fractionation showed that H2O-extractable P was the predominant form in broiler litter (56-77%), whereas aqueous phosphate determined with XANES was <18% indicating that H2O probably dissolved mineral forms of P (e.g., dicalcium phosphate). Results show that HCl extraction primarily removed phytic acid from broiler litters and normal turkey manure, while it removed a mixture of hydroxylapatite and phytic acid from modified turkey manures. The combination of chemical fractionation and XANES provided information about the nature of P in these manures, which may help to devise best management practices for manure use.     

Changes in heavy metal contents in animal feeds and manures in an intensive animal production region of China

The 360 feed and manure samples were collected from 150 animal farms in Jiangsu Province, China and analyzed for heavy metals. Concentrations of Zn and Cu in animal feeds were 15.9-2041.8 and undetected-392.1 mg/kg respectively, while Hg, As, Pb, Cd, and Cr in all feeds were below 10 mg/kg. Concentrations of Cu, Zn, and Cr in animal manures were 8.4-1726, 39.5-11379, and 1.0-1602 mg/kg respectively, while As, Cd, Hg, and Pb were 〈 10 mg/kg. The concentration of Cu, Zn, As and Cr in animal feed and manure were positively correlated （p 〈 0.001）, but the Cd, Hg, and Pb were not statistically correlated between the feed and the manure. Concentrations of Cu and Zn were highest in pig feed and manure, followed by poultry and dairy feeds and manures. During 1990- 2008, Cu, Zn, As, Cr, Cd contents increased by 771%, 410%, 420%, 220%, and 63% in pig manure, 212%, 95%, 200%, 791%, and -63% in dairy manure, and 181%, 197%, 1500%, 261, and 196% in poultry manure. Most of the increases occurred from 2002 to 2008, which reflects the extensive use of feed additives after 2002. In contrast, Pb and Hg in manures continuously decreased from 1990 to 2008. The results suggest that the heavy metal contents in animal manure have been greatly increased over 18 years and the contribution of manures to soil should be considered.     

Comparison of phosphorus forms in wet and dried animal manures by solution phosphorus-31 nuclear magnetic resonance spectroscopy and enzymatic hydrolysis

Both enzymatic hydrolysis and solution (31)P nuclear magnetic resonance (NMR) spectroscopy have been used to characterize P compounds in animal manures. In this study, we comparatively investigated P forms in 0.25 M NaOH/0.05 M EDTA extracts of dairy and poultry manures by the two methods. For the dairy manure, enzymatic hydrolysis revealed that the majority of extracted P was inorganic P (56%), with 10% phytate-like P, 9% simple monoester P, 6% polynucleotide-like P, and 18% non-hydrolyzable P. Similar results were obtained by NMR spectroscopy, which showed that inorganic P was the major P fraction (64-73%), followed by 6% phytic acid, 14 to 22% other monoesters, and 7% phosphodiesters. In the poultry manure, enzymatic hydrolysis showed that inorganic P was the largest fraction (71%), followed by 15% phytate-like P and 1% other monoesters, and 3% polynucleotide-like P. NMR spectroscopy revealed that orthophosphate was 51 to 63% of extracted P, phytic acid 24 to 33%, other phosphomonoesters 6 to 12%, and phospholipids and DNA 2% each. Drying process increased orthophosphate (8.4% of total P) in dairy manure, but decreased orthophosphate (13.3% of total P) in poultry manure, suggesting that drying treatment caused the hydrolysis of some organic P to orthophosphate in dairy manure, but less recovery of orthophosphate in poultry manure. Comparison of these data indicates that the distribution patterns of major P forms in animal manure determined by the two methods were similar. Researchers can utilize the method that best fits their specific research goals or use both methods to obtain a full spectrum of manure P characterization.     

Effect of tomato packinghouse wastewater properties on phosphorus and cation leaching in a spodosol

Land application of wastewater is a common practice. However, coarse-textured soils and shallow groundwater in Florida present favorable conditions for leaching of wastewater-applied constituents. Our objective in this study was to determine phosphorus (P) and associated cations (Ca, Mg, K, Na) leaching in a Spodosol irrigated with tomato packinghouse wastewater. We packed 12 polyvinyl chloride soil columns (30 cm internal diameter × 50 cm length) with two soil horizons (Ap and A/E) and conducted 30 sequential leaching events by irrigating with wastewater at low (0.84 cm d), medium (1.68 cm d), and high (2.51 cm d) rates. The control treatment received deionized water at 1.68 cm d Leachate pH was lower (6.4-6.5) and electrical conductivity (EC) was higher in the wastewater-treated columns (0.85-1.78 dS m) than in the control treatment (pH 6.9; EC, 0.12 dS m) due to the low pH (6.2) and high EC (2.16 dS m) of applied wastewater. Mean leachate P concentrations were greatest in the control treatment (0.70 mg L), followed by the high (0.60 mg L) and low and medium wastewater-treated columns (0.28-0.33 mg L). Leachate concentrations of Na, Ca, Mg, and K were significantly ( < 0.05) greater in wastewater-treated columns than in the control. Concentrations of P, Na, and K in leachate remained lower than the concentrations in the applied wastewater, indicating their retention in the soil profile. In contrast, leachate Ca and Mg concentrations were greater than in applied wastewater during several leaching events, suggesting that additional Ca and Mg were leached from the soil. Our results suggest that tomato packinghouse wastewater can be beneficially land-applied at 1.68 cm d in Florida's Spodosols without significant P and cation leaching.     

Evaluation of regression methodology with low-frequency water quality sampling to estimate constituent loads for ephemeral watersheds in Texas

Water quality regulation and litigation have elevated the awareness and need for quantifying water quality and source contributions in watersheds across the USA. In the present study, the regression method, which is typically applied to large (perennial) rivers, was evaluated in its ability to estimate constituent loads (NO(3)-N, total N, PO(4)-P, total P, sediment) on three small (ephemeral) watersheds with different land uses in Texas. Specifically, regression methodology was applied with daily flow data collected with bubbler stage recorders in hydraulic structures and with water quality data collected with four low-frequency sampling strategies: random, rise and fall, peak, and single stage. Estimated loads were compared with measured loads determined in 2001-2004 with an autosampler and high-frequency sampling strategies. Although annual rainfall and runoff volumes were relatively consistent within watersheds during the study period, measured annual nutrient and sediment concentrations and loads varied considerably for the cultivated and mixed watersheds but not for the pasture watershed. Likewise, estimated loads were much better for the pasture watershed than the cultivated and mixed landuse watersheds because of more consistent land management and vegetation type in the pasture watershed, which produced stronger correlations between constituent loads and mean daily flow rates. Load estimates for PO(4)-P were better than for other constituents possibly because PO(4)-P concentrations were less variable within storm events. Correlations between constituent concentrations and mean daily flow rate were poor and not significant for all watersheds, which is different than typically observed in large rivers. The regression method was quite variable in its ability to accurately estimate annual nutrient loads from the study watersheds; however, constituent load estimates were much more accurate for the combined 3-yr period. Thus, it is suggested that for small watersheds, regression-based annual load estimates should be used with caution, whereas long-term estimates can be much more accurate when multiple years of concentration data are available. The predictive ability of the regression method was similar for all of the low-frequency sampling strategies studied; therefore, single-stage or random strategies are recommended for low-frequency storm sampling on small watersheds because of their simplicity.     

UV-H2O2 based AOP and its integration with biological activated carbon treatment for DBP reduction in drinking water

The presence of disinfection byproducts (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs) in drinking water is of great concern due to their adverse effects on human health. Emerging regulation limiting the concentration of DBPs in drinking water has increased demands for technologies and processes which reduce the formation of DBPs in drinking water. In this study, UV-H₂O₂ based advance oxidation process (AOP) was used to treat raw surface water. Experiments were conducted using low pressure mercury vapor UV lamps in collimated beam and flow-through annular photoreactors. The effect of UV fluence (0–3500 mJ cm⁻²) and hydrogen peroxide concentration (0–23 mg l⁻¹) in reducing the concentration of THMs and HAAs was examined. The UV-H₂O₂ AOP was then coupled with a downstream biological activated carbon (BAC) treatment to assess the synergetic benefits of combining the two treatments. It was observed that UV-H₂O₂ AOP was only effective at reducing DBPs at UV fluences of more than 1000 mJ cm⁻²and initial H₂O₂ concentrations of about or greater than 23 mg l⁻¹. However, the combined AOP–BAC treatment showed significant reductions of 43%, 52%, and 59% relative to untreated raw water for DBPs, TOC, and UV₂₅₄, respectively.     

Phosphorus exchangeability and leaching losses from two grassland soils

Although phosphate phosphorus (P) is strongly sorbed in many soils, it may be quickly transported through the soil by preferential flow. Under flood irrigation, preferential flow is especially pronounced and associated solute losses may be important. Phosphorus losses induced by flood irrigation were investigated in a lysimeter study. Detailed soil chemical analyses revealed that P was very mobile in the topsoil, but the higher P-fixing capacity of the subsoil appeared to restrict P mobility. Application of a dye tracer enabled preferential flow pathways to be identified. Soil sampling according to dye staining patterns revealed that exchangeable P was significantly greater in preferential flow areas as compared with the unstained soil matrix. This could be partly attributed to the accumulation of organic carbon and P, together with enhanced leaching of Al- and Fe-oxides in the preferential flow areas, which resulted in reduced P sorption. The irrigation water caused a rapid hydrologic response by displacement of resident water from the subsoil. Despite the occurrence of preferential flow, most of the outflowing water was resident soil water and very low in P. In these soils the occurrence of preferential flow per se is not sufficient to cause large P losses even if the topsoil is rich in P. It appears that the P was retained in lower parts of the soil profile characterized by a very high P-fixing capacity. This study demonstrates the risks associated with assessing potential P losses on the basis of P mobility in the topsoil alone.     

Establishing a linkage between phosphorus forms in dairy diets, feces, and manures

Effective manure management to efficiently utilize organic wastes without causing environmental degradation requires a clear understanding of the transformation of P forms from diet to manure. Thus, the objective of this study was to establish quantitative relationships between P forms in diets, feces, and manures collected from U.S. Northeastern and Mid-Atlantic commercial dairy farms. Total P in diets ranged from 3.6 to 5.3 g kg(-1) dry matter, while the feces had higher P than diets (5.7-9.5 g kg(-1)) and manures had lower P (2.5-8.9 g kg(-1)) than feces. The farms with total dietary P of 4.8 to 5.3 g P kg(-1) had twofold higher concentrations of phytic acid (1647-2300 mg P kg(-1)) than farms with 3.6 to 4.0 g dietary P kg(-1) (844-1100 mg P kg(-1)). Much of the phytic acid in diets was converted to inorganic orthophosphate in the rumen as indicated by a reduction in phytic acid percentage from diets (32%) to feces (18%). The proportion of orthophosphate diesters (phospholipids, deoxyribonucleic acid [DNA]) was twice as high in feces (6.2-10%) as diets (2.4-5.3%) suggesting the excretion of microbial residues in feces. Phosphonates (aminoethyl phosphonates and phosphonolipids) were not seen in diets but were detected in feces and persisted in manures, which suggests a microbial origin. These organic compounds (phytic acid, phospholipids, DNA) were decomposed on storage of feces in slurry pits, increasing orthophosphate in manures by 9 to 12% of total P. These results suggest that reducing dietary P and typically storing feces in dairy farms will result in manure with similar chemical forms (primarily orthophosphate: 63-77%) that will be land applied. Thus, both the reduction of dietary P and storage of manure on farm are important for controlling solubility and bioavailability of P forms in soils and waters.     

Selection of a water-extractable phosphorus test for manures and biosolids as an indicator of runoff loss potential

The correlation of runoff phosphorus (P) with water-extractable phosphorus (WEP) in land-applied manures and biosolids has spurred wide use of WEP as a water quality indicator. Land managers, planners, and researchers need a common WEP protocol to consistently use WEP in nutrient management. Our objectives were to (i) identify a common WEP protocol with sufficient accuracy and precision to be adopted by commercial testing laboratories and (ii) confirm that the common protocol is a reliable index of runoff P. Ten laboratories across North America evaluated alternative protocols with an array of manure and biosolids samples. A single laboratory analyzed all samples and conducted a separate runoff study with the manures and biosolids. Extraction ratio (solution:solids) was the most important factor affecting WEP, with WEP increasing from 10:1 to 100:1 and increasing from 100:1 to 200:1. When WEP was measured by a single laboratory, correlations with runoff P from packed soil boxes amended with manure and biosolids ranged from 0.79 to 0.92 across all protocol combinations (extraction ratio, filtration method, and P determination method). Correlations with P in runoff were slightly lower but significant when WEP was measured by the 10 labs (r=0.56-0.86). Based on laboratory repeatability and water quality evaluation criteria, we recommend the following common protocol: 100:1 extraction ratio; 1-h shaking and centrifuge 10 min at 1500xg (filter with Whatman #1 paper if necessary); and determining P by inductively coupled plasma-atomic emission spectrometry or colorimetric methods.     

Methoxyphenols from burning of Scandinavian forest plant materials

Semivolatile compounds in smoke from gram-scale incomplete burning of plant materials were assessed by gas chromatography and mass spectrometry. Gas syringe sampling was shown to be adequate by comparison with adsorbent sampling. Methoxyphenols as well as 1,6-anhydroglucose were released in amounts as large as 10 mg kg(-1) of dry biomass at 90% combustion efficiency. Wood, twigs, bark and needles from the conifers Norway spruce and Scots pine emitted 12 reported 2-methoxyphenols in similar proportions. Grass, heather and birchwood released the same 2-methoxyphenols but also the corresponding 2,6-dimethoxyphenols which are characteristic of angiosperms. The methoxyphenols are formed from lignin and differ in structure by the group in para position relative to the phenolic OH group. Prominent phenols were those with trans-1-propenyl and ethenyl groups in that position. Vanillin, 4-hydroxy-3-methoxybenzaldehyde, was a prominent carbonyl compound from the conifer materials.