Effects of freeze-thaw cycles on distribution and speciation of heavy metals in pig manure.

To understand the potential environmental influence of animal manure under freeze-thaw cycles, pig manure was used to conduct a simulation experiment to explore the effects of freeze-thaw cycles on heavy metal distribution and form transformation. Thirty cycles of freezing and thawing were performed alternately by freezing at - 18 ± 2 °C for 24 h and thawing at 20 ± 2 °C for 24 h. By a serial wet sieving procedure, manure samples were separated into different sizes of 1000, 250, 75, 38, and < 38 μm. Solid samples were collected from the dry matter at each stage of sieve; then the washing waters were collected as liquid samples accordingly. The concentrations of heavy metals in solid/liquid samples and their five forms were analyzed. It showed that the concentrations of heavy metals in the solid and liquid samples gradually increased because of organic matter degradation during freezing and thawing cycles. The distribution of heavy metals on particles of different sizes was also affected by the degradation and breakup of pig manure; the metals showed a tendency to aggregate in small particles (< 38 μm). Among them, the percentage of Cu and Zn on < 38 μm particles increased by 162.3% and 554.1%, respectively. After several freeze-thaw cycles, the concentrations of EXCH-X (metals of exchangeable form) increased significantly, those of CARB-X (carbonate-bound form) and Fe/Mn-X (Fe/Mn oxide-bound form) decreased accordingly. These form transformations may be largely influenced by the enhancement of dissolved organic matter (DOM) and the reduction of pH value. Therefore, frequent freeze-thaw cycles may promote the mobility and bioavailability of heavy metals in pig manure. The results are significant for understanding the pollution risk of pig manure in the freeze-thaw regions.