『(Abstract)
Intensive manure application is an important source of diffuse
phosphorus (P) pollution. Phosphorus availability from animal
manure is influenced by its chemical speciation. The major objective
of this study was to investigate the P speciation in raw and anaerobically
digested dairy manure with an emphasis on the calcium (Ca) and
magnesium (Mg) phosphate phases. Influent and effluent from an
on-farm digester in Wisconsin were sampled and sieved, and the
25 to 53μm size fraction was dried for X-ray powder diffraction
(XRD) and P K-edge X-ray absorption near edge structure (XANES)
analyses. Struvite (MgNH4PO4・6H2O) was identified in both the raw (influent)
and anaerobically digested (effluent) manure using XRD. Qualitative
analysis of P K-edge XANES spectra indicated that the Ca orthophosphate
phases, except dicalcium phosphate anhydrous (DCPA) or monetite
(CaHPO4), were not abundant in dairy manure.
Linear combination fitting (LCF) of the P standard compounds showed
that 57.0 and 43.0% of P was associated with DCPA and struvite,
respectively, in the raw manure. In the anaerobically digested
sample, 78.2% of P was present as struvite and 21.8% of P was
associated with hydroxylapatite (HAp). The P speciation shifted
toward Mg orthophosphates and least soluble Ca orthophosphates
following anaerobic digestion. Similarity between the aqueous
orthophosphate (aq-PO4), newberyite (MgHPO4・3H2O), and struvite spectra
can cause inaccurate P speciation determination when dairy manure
is analyzed solely using P K-edge XANES spectroscopy; however,
XANES can be used in conjunction with XRD to quantify the distribution
of inorganic P species in animal manure.』
Abbreviation
(Introduction)
Materials and methods
Sample collection and characterization
X-ray powder diffraction analysis
X-ray absorption near-edge structure analysis
Phosphorus standards
Data collection and pre-treatment
Results and discussion
X-ray powder diffractograms of manure samples
Qualitative XANES analysis of phosphorus standards and manure
samples
Least squares linear combination fitting of the XANES data
Environmental implications of manure phosphorus speciation
Probable improvements in the XANES and XRD methods
Conclusions
Acknowledgments
References