title: Changes in chlorinated organic pollutants and heavy metal content of sediments during pyrolysis.
abstract: BACKGROUND
  There has been an increasing concern about the treatment and disposal of contaminated sediment from dredged rivers, harbors or estuaries due to the accumulated toxic organics such as dioxins and inorganics, particularly heavy metals like Cr, Pb, Zn, Cu, Hg and Cd. However, considering the huge amount of materials and financial costs involved, any candidate technology must ultimately result in reusable, residual by-products. This can only be made possible if the toxic pollutants are removed or stabilized in the raw sediment and then fed back into the materials cycle. Currently, we are developing a pyrolysis process for the commercial-scale cleanup of dioxins and heavy metal-contaminated river sediment to yield reusable char for various economical applications. In this connection, this paper describes our preliminary investigation into the extent of dioxins and heavy metal volatilization from actual contaminated sediment. The stabilization of certain metallic species, particularly Cr ions, was studied.
  
  
  METHODS
  Laboratory scale pyrolysis experiments were conducted using a special, horizontal lab-scale pyrolyzer. Sediment samples from Shanghai Suzhou Creek and Tagonoura harbor were pyrolyzed in the reactor under nitrogen gas at 800 degrees C and different retention times of 30, 60 and 90 min. A constant heating rate of 10 degrees C min(-1) was employed. The pyrolysis gas was first allowed to pass through a cold trap to condense the tar. Uncondensed gases were then channeled through a column containing an adsorbent (XAD-2 Resin) for dioxins. Heavy metal concentrations in the initial and final sediment residues were analyzed by ICP (Nippon Jarrel-Ash) following their acid and alkali (for Cr6+) digestion. Dioxin contents of the pyrolysis char, tar, and exhaust gases in the dioxin adsorbent were also determined. For comparative purpose, thermal treatment under air flow was conducted.
  
  
  RESULTS
  The data for the removal of heavy metals from Suzhou Creek sediment showed very significant reductions in Pb, Zn and Cr6+ content of the sediment at this condition. Percentage removals were 42.4%, 60.8% and 42.2%, respectively. The disappearance of Cr6+ was due to reduction reactions rather than volatilization, since the total Cr content remained almost unchanged. Other heavy metals such as Cu, Fe and Ni showed very minimal reductions. Nonetheless, Toxicity Characteristics Leaching Procedure (TCLP) tests confirmed that these residual heavy metals were rather stable in the pyrolysis char. Reduction of toxic Cr6+ at 42.2% has also been achieved by pyrolysis (with N2) as opposed to the more than 580% increase in Cr6+ observed during thermal oxidation (with air).
  
  
  CONCLUSIONS
  Pyrolysis also removes toxic organics, particularly dioxins, from the sediment. For the total dioxins, removal percentage of 99.9999% was achieved even at the lowest retention time of 30 min. Almost all polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) were removed at any retention time. The TEQs detected from the solid residues were mainly contributed by dioxin-like PCBs, yet these were present in relatively trace quantities. At the shortest retention time of 30 min, only 0.000085 pg-TEQ g(-1) of polychlorinated biphenyls (PCBs) was detected in the pyrolysis char. Furthermore, the residual PCBs have very low toxicity ratings and none of the highly toxic PCBs, which were initially present in the sediment such as 3,3',4,4',5-PeCB and 3,3',4,4'5,5'-HxCB, were detected in the char. Results further confirmed that most of the dioxins that were removed were transferred to the gas phase so that volatilization may be considered as the main mechanism for their removal.
  
  
  CONCLUSIONS
  Some heavy metals, particularly Pb and Zn, can be volatilized under N2 pyrolysis at 800 degrees C. Pyrolysis also prevented the formation of more toxic Cr6+ ions and, at the same time, resulted in its reduction by around 42.2%, in contrast to the 580% increase during thermal oxidation. PCDDs and PCDFs have been removed and were not formed in the solid products over the retention time range of 30-90 min at 800 degrees C. Dioxin-like PCBs mostly remained and a retention time of 30 min was found to be sufficient for its maximum removal. Recommendations and Perspectives. With the above results, a temperature of 800 degrees C at a retention time of 30 min is sufficient for the removal of total dioxins and of some heavy metals by volatilization. It is, however, necessary to destroy the dioxins as well as recover heavy metals in the gas phase. Stability of remaining heavy metals in the char also needs to be confirmed by leaching tests. These are the major concerns, which we are currently evaluating in order to establish the feasibility of our proposed, large scale pyrolysis system for sediment treatment.
authors.affiliation: School of Environmental Science and Engineering, Shanghai Jiaotong University, 800 Dongchuan Road, Shanghai 200240, P.R. China.
authors.forename: Zhanbo
authors.initials: Z
authors.lastname: Hu
authors.forename: Ronald
authors.initials: R
authors.lastname: Navarro
authors.forename: Nakao
authors.initials: N
authors.lastname: Nomura
authors.forename: Hainan
authors.initials: H
authors.lastname: Kong
authors.forename: Saman
authors.initials: S
authors.lastname: Wijesekara
authors.forename: Masatoshi
authors.initials: M
authors.lastname: Matsumura
mesh_terms: D002681:China; D006801:Humans; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D019216:Metals, Heavy / Q000737:chemistry*; D045483:Rivers; D012989:Soil Pollutants / Q000737:chemistry*; D018505:Waste Management / Q000379:methods*
chemical_list: D006843:Hydrocarbons, Chlorinated; D019216:Metals, Heavy; D012989:Soil Pollutants