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Xinan Zhang
             Research Assistant
Louisiana Forest Products Development Center
   School of Renewable Natural Resources
          Louisiana State University




                              FPS 65th International Conference
Introduction
 Chromate Copper Arsenate (CCA)
-- an inorganic waterborne wood preservative

 There was a rapid expansion of the use of CCA
 wood preservative between 1975 and 1990, as a
 result of high consumer acceptance of the product
 for decks, fences and other residential applications
 and industrial products such as poles, timbers and
 marine piling.
Introduction
 The US and Canadian wood preservation industry voluntarily
  withdraw the use of CCA treated wood for residential uses on
  January 1, 2004


 Currently, most of the out-of-service treated wood ends up in
  landfills.
                   (diffusion into soil and ground water?)


 It is estimated that CCA-treated wood being removed from service
  annually in the US would increase to 16x106 m3 by 2020 (Copper
  1993).
Introduction
     Management of spent treated wood products

To recycle spent CCA treated wood
 (1) Burning            (diffusion into air ?)
 (2) Reuse to make composites
 (3) Biological detoxification
 (4) Chemical extraction prior to disposal or recycling
Literature Review
 Kartal et al. (2008) evaluated the effects of various
 adsorbents (activated carbon, Sugi wood charcoal)
 from industrial and agricultural process in removal of
 Cu, Cr, As from CCA treated wood by using bath
 extracting experiments.

 Kartal and Imamura (2005) found that exposing 3g
 CCA-treated sawdust to a 200 ml solution containing
 2.5 g chitin (biopolymer) for 10 days removed 74%
 Cu, 62% Cr and 63% As.
Literature Review
 Extraction with 1% ethylenediaminetetracetic acid (EDTA)
  solution for 24 h of sawdust samples results in 93% Cu, 36%
  Cr and 38% As removal (Kartal, S. N. 2003).

 CCA treated wood can be decontaminated to a high degree by
  10% aqueous hydrogen peroxide (H2O2) at 50℃ water bath
  and 6h. 95% Cr, 94% Cu, 98% As were removed. (Kazi and
  Cooper 2006).

 Clausen and Smith (1998) found that extraction with oxalic
  acid as a precursor to bacterial fermentation with B.
  licheniformis CC01 removed 90% Cu, 80% Cr and 100% As
  from treated chips.
Literature Review
Kazi and Cooper (2002) extracted CCA from sludge in
three stages,
 (1) simultaneous extraction and oxidation by
  aqueous sodium hypochlorite (5.25%), 2h, 100℃,
  R:S 100 recover 51%
 (2) extraction of the remaining CCA salts by
  phosphoric acid (2.5%)       rest components were
  removed after 2h, 100℃ and R:S 100
 (3) oxidation of phosphoric acid leachate by aqueous
  sodium hypochlorite (5.25%).
Key point
Treatment time


Cost – chemical
Objective
 Evaluate the effect of acid extraction microwave
 treatment

 Investigate the possibility of reusing the soaking
 solution

 Evaluation of antifungal activities of recycled
 soaking solution against white-rot and brown-rot
 fungi
Material and Method
              Wood particles preparation
                                      cut into small
a piece of retired utility
                                      pieces
pole



ground in a Wiley Mill
                                        air dried




The wood particles which passed the 40-mesh sieve were
collected
Material and Method
 Acid preparation

                        1:1        acetic acid
   phosphoric acid
       2.75%                         0.75%




                     mixed acids
Material and Method
 microwave extraction

       1 g CCA-treated       vs   20 ml acids
       waste wood particle




 microwave reactor (Milestone, Sheton, CT)


     treatment time                  temperature
         20 min                         145℃.
Material and Method
   Reuse extraction liquids
microwave      vaccum filter the      collect extraction   measure the
treatment      extraction liquid Ⅰ    liquid Ⅰ             volume

                               made up lost volume by fresh       analysis of CCA
A new batch of wood
                               mixed acids to obtain the          concentration
powder was added to
                               cycle 2 acids
cycle 2 acids


microwave      vaccum filter the      collect extraction      measure the
treatment      extraction liquid Ⅱ    liquid Ⅱ                volume


                            made up lost volume by fresh
  ……..                      mixed acids to obtain the           analysis of CCA
                            cycle 3 acids                       concentration
Material and Method
   Determination of copper, chromium and arsenic
    concentrations

rinse wood residue                                1 g wood residue and 15
                        oven dried
of each cycle with                                ml nitric acid was mixed
deionized (DI) water                              in a 100 ml test tube
                        obtain a transparent
                        liquid, heat to a
                        volume of 1 ml,                 slowly warmed and
Quantitative
                        transfer into a 25 ml           maintain temperature
elemental analysis of
                        volumetric flask and            at120 ℃
copper, chromium
                        diluted into 25 ml
and arsenic
                        solution with distilled
                        water
Material and Method
 Evaluation of antifungal activities against white-rot (
  Trametes    versicolor)             and       brown-rot         fungi
  (Gloeophyllum trabeum)


malt extract medium
-- 2% malt extract, 1.5% agar and 0.005% yeast extract


extraction liquid 1
--mixed into 100 ml media to make a series of solutions with different
  concentrations
Material and Method




Where D2 is the diameter growth in the control dishes and D1 is
diameter growth in the experimental Petri dishes with extract liquids.
The estimation of antifungal activities was carried out with repetition.
Result and discussion
                           1000

                           900

                           800
                                                                                              As
  Concentration (mg L-1)




                           700

                           600
                                                                                              Cr
                           500

                           400
                                                                                              Cu
                           300

                           200

                            100

                             0
                                  1    2   3   4   5   6           7   8   9   10   11   12
                                                           Cycle




Fig. 1. The concentration of Arsenic (As), Chromium (Cr) and Copper (Cu) in each
   extraction liquid of each cycle (unit: ppm)
Result and discussion
                    100

                    90

                    80

                    70
Recovery rate (%)




                    60

                    50                                                                             AS
                                                                                                   Cr
                    40
                                                                                                   Cu
                    30

                    20

                     10

                     0
                                1                 2                      3            4
                                                      Extraction cycle



                      Fig. 2. The recovery rate of Arsenic (As), Chromium (Cr) and Copper (Cu) in wood
                         residue from first 4 cycle
Result and discussion
Table 1. The everyday fungal growth rate of TV




concentration                                day

   (mg L-1)      2       3          4            5    7      8      9
   control      1.65    2.45       3.5       4.5     6.6    7.55    8.7
    1.92        1.1      1.8       2.5       3.2     4.7    5.65    6.3
    2.53         1       1.7       2.2       2.8     4.1    4.8     5.4
    2.84        0.95     1.5       1.9       2.5     3.7    4.4     5
    3.15        0.95     1.4       1.8       2.4     3.45    4      4.5
    3.45        0.8      1.2       1.55          2   2.95   3.45    3.8
    3.76        0.65    1.05       1.45      1.9     2.65   3.2     3.6
    4.06         -      0.805       1        1.2     1.7     2      2.2
    4.36         -        -        0.7       0.9     1.3    1.5    1.65
    4.66         -        -         -        0.65    0.85    1      1.1
    4.96         -        -         -            -   0.8    0.9    0.975
    5.55         -        -         -            -    -      -      0
Result and discussion
Table 2. The everyday fungal growth rate of GT


  concentration                                             day
     (mg L-1)      2      3      4      5      7      8      9     10     12     14     16     18     19
     control      1.25   1.90   2.60   2.85   3.85   4.35   4.90   5.30   6.15   6.90   7.40   7.80   8.70
      1.92        0.88   1.25   1.70   2.05   2.85   3.25   3.60   3.95   4.65   5.10   5.65   6.00   6.25
      2.53        0.75   1.05   1.30   1.68   2.20   2.50   2.80   3.10   3.65   4.00   4.55   4.80   5.05
      2.84        0.73   1.00   1.30   1.60   2.10   2.45   2.70   3.00   3.45   3.90   4.40   4.70   4.85
      3.15        0.65   0.90   1.10   1.40   1.90   2.20   2.40   2.70   3.10   3.60   4.00   4.25   4.55
      3.45        0.70   0.90   1.10   1.40   1.80   2.10   2.30   2.60   2.95   3.30   3.70   3.95   4.15
      3.76         -     0.70   0.90   1.00   1.55   1.75   1.95   2.10   2.45   2.85   3.30   3.50   3.75
      4.06         -     0.80   1.00   1.20   1.60   1.75   1.95   2.10   2.45   2.75   3.10   3.30   3.45
      4.36         -      -     0.80   0.95   1.20   1.40   1.50   1.75   2.00   2.25   2.50   2.70   2.80
      4.66         -      -     0.70   0.80   1.00   1.20   1.30   1.40   1.70   1.90   2.05   2.20   2.35
      4.96         -      -      -     0.80   1.00   1.15   1.30   1.40   1.60   1.80   2.00   2.10   2.30
      5.55         -      -      -     0.65   0.80   0.90   1.00   1.10   1.30   1.50   1.75   1.90   2.00
      6.14         -      -      -      -     0.65   0.75   0.85   0.95   1.15   1.40   1.60   1.80   1.90
       7.3         -      -      -      -      -      -      -      -      -      -      -      -      0
Result and discussion




Fig. 3. Antifungal effects of cycle 1 extraction liquid from different concentration (white rot fungi)
Result and discussion




Fig. 4. Antifungal effects of cycle 1 extraction liquid from different concentration brown rot fungi)
Result and discussion
                   100

                        90

                        80
Anti fungal index (%)




                        70

                        60

                        50
                                                                                                                                       TV
                        40                                                                                                             GT

                        30

                        20

                        10

                        0
                             1.92   2.53   2.84   3.15   3.45   3.76   4.06   4.36   4.66   4.96   5.55   6.14   7.30   9.55   11.72
                                                         Copper concentration in medium (mg L-1)




                         Fig. 5. Plots of antifungal index (AI) versus copper concentration
Summary
 Acid extraction microwave treatment is a fast and
 effective method to remove Cu, Cr and As from
 CCA-treated waste wood.

 Soaking solution has the potential to continue
 remove Cu, Cr and As from CCA-treated waste
 wood.

 Soaking solution showed the antifungal activities
 against white-rot and brown-rot fungi.
Thank you

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Session 28 ic2011 zhang

  • 1. Xinan Zhang Research Assistant Louisiana Forest Products Development Center School of Renewable Natural Resources Louisiana State University FPS 65th International Conference
  • 2. Introduction  Chromate Copper Arsenate (CCA) -- an inorganic waterborne wood preservative  There was a rapid expansion of the use of CCA wood preservative between 1975 and 1990, as a result of high consumer acceptance of the product for decks, fences and other residential applications and industrial products such as poles, timbers and marine piling.
  • 3. Introduction  The US and Canadian wood preservation industry voluntarily withdraw the use of CCA treated wood for residential uses on January 1, 2004  Currently, most of the out-of-service treated wood ends up in landfills. (diffusion into soil and ground water?)  It is estimated that CCA-treated wood being removed from service annually in the US would increase to 16x106 m3 by 2020 (Copper 1993).
  • 4. Introduction Management of spent treated wood products To recycle spent CCA treated wood  (1) Burning (diffusion into air ?)  (2) Reuse to make composites  (3) Biological detoxification  (4) Chemical extraction prior to disposal or recycling
  • 5. Literature Review  Kartal et al. (2008) evaluated the effects of various adsorbents (activated carbon, Sugi wood charcoal) from industrial and agricultural process in removal of Cu, Cr, As from CCA treated wood by using bath extracting experiments.  Kartal and Imamura (2005) found that exposing 3g CCA-treated sawdust to a 200 ml solution containing 2.5 g chitin (biopolymer) for 10 days removed 74% Cu, 62% Cr and 63% As.
  • 6. Literature Review  Extraction with 1% ethylenediaminetetracetic acid (EDTA) solution for 24 h of sawdust samples results in 93% Cu, 36% Cr and 38% As removal (Kartal, S. N. 2003).  CCA treated wood can be decontaminated to a high degree by 10% aqueous hydrogen peroxide (H2O2) at 50℃ water bath and 6h. 95% Cr, 94% Cu, 98% As were removed. (Kazi and Cooper 2006).  Clausen and Smith (1998) found that extraction with oxalic acid as a precursor to bacterial fermentation with B. licheniformis CC01 removed 90% Cu, 80% Cr and 100% As from treated chips.
  • 7. Literature Review Kazi and Cooper (2002) extracted CCA from sludge in three stages,  (1) simultaneous extraction and oxidation by aqueous sodium hypochlorite (5.25%), 2h, 100℃, R:S 100 recover 51%  (2) extraction of the remaining CCA salts by phosphoric acid (2.5%) rest components were removed after 2h, 100℃ and R:S 100  (3) oxidation of phosphoric acid leachate by aqueous sodium hypochlorite (5.25%).
  • 9. Objective  Evaluate the effect of acid extraction microwave treatment  Investigate the possibility of reusing the soaking solution  Evaluation of antifungal activities of recycled soaking solution against white-rot and brown-rot fungi
  • 10. Material and Method Wood particles preparation cut into small a piece of retired utility pieces pole ground in a Wiley Mill air dried The wood particles which passed the 40-mesh sieve were collected
  • 11. Material and Method  Acid preparation 1:1 acetic acid phosphoric acid 2.75% 0.75% mixed acids
  • 12. Material and Method  microwave extraction 1 g CCA-treated vs 20 ml acids waste wood particle  microwave reactor (Milestone, Sheton, CT) treatment time temperature 20 min 145℃.
  • 13. Material and Method  Reuse extraction liquids microwave vaccum filter the collect extraction measure the treatment extraction liquid Ⅰ liquid Ⅰ volume made up lost volume by fresh analysis of CCA A new batch of wood mixed acids to obtain the concentration powder was added to cycle 2 acids cycle 2 acids microwave vaccum filter the collect extraction measure the treatment extraction liquid Ⅱ liquid Ⅱ volume made up lost volume by fresh …….. mixed acids to obtain the analysis of CCA cycle 3 acids concentration
  • 14. Material and Method  Determination of copper, chromium and arsenic concentrations rinse wood residue 1 g wood residue and 15 oven dried of each cycle with ml nitric acid was mixed deionized (DI) water in a 100 ml test tube obtain a transparent liquid, heat to a volume of 1 ml, slowly warmed and Quantitative transfer into a 25 ml maintain temperature elemental analysis of volumetric flask and at120 ℃ copper, chromium diluted into 25 ml and arsenic solution with distilled water
  • 15. Material and Method  Evaluation of antifungal activities against white-rot ( Trametes versicolor) and brown-rot fungi (Gloeophyllum trabeum) malt extract medium -- 2% malt extract, 1.5% agar and 0.005% yeast extract extraction liquid 1 --mixed into 100 ml media to make a series of solutions with different concentrations
  • 16. Material and Method Where D2 is the diameter growth in the control dishes and D1 is diameter growth in the experimental Petri dishes with extract liquids. The estimation of antifungal activities was carried out with repetition.
  • 17. Result and discussion 1000 900 800 As Concentration (mg L-1) 700 600 Cr 500 400 Cu 300 200 100 0 1 2 3 4 5 6 7 8 9 10 11 12 Cycle Fig. 1. The concentration of Arsenic (As), Chromium (Cr) and Copper (Cu) in each extraction liquid of each cycle (unit: ppm)
  • 18. Result and discussion 100 90 80 70 Recovery rate (%) 60 50 AS Cr 40 Cu 30 20 10 0 1 2 3 4 Extraction cycle Fig. 2. The recovery rate of Arsenic (As), Chromium (Cr) and Copper (Cu) in wood residue from first 4 cycle
  • 19. Result and discussion Table 1. The everyday fungal growth rate of TV concentration day (mg L-1) 2 3 4 5 7 8 9 control 1.65 2.45 3.5 4.5 6.6 7.55 8.7 1.92 1.1 1.8 2.5 3.2 4.7 5.65 6.3 2.53 1 1.7 2.2 2.8 4.1 4.8 5.4 2.84 0.95 1.5 1.9 2.5 3.7 4.4 5 3.15 0.95 1.4 1.8 2.4 3.45 4 4.5 3.45 0.8 1.2 1.55 2 2.95 3.45 3.8 3.76 0.65 1.05 1.45 1.9 2.65 3.2 3.6 4.06 - 0.805 1 1.2 1.7 2 2.2 4.36 - - 0.7 0.9 1.3 1.5 1.65 4.66 - - - 0.65 0.85 1 1.1 4.96 - - - - 0.8 0.9 0.975 5.55 - - - - - - 0
  • 20. Result and discussion Table 2. The everyday fungal growth rate of GT concentration day (mg L-1) 2 3 4 5 7 8 9 10 12 14 16 18 19 control 1.25 1.90 2.60 2.85 3.85 4.35 4.90 5.30 6.15 6.90 7.40 7.80 8.70 1.92 0.88 1.25 1.70 2.05 2.85 3.25 3.60 3.95 4.65 5.10 5.65 6.00 6.25 2.53 0.75 1.05 1.30 1.68 2.20 2.50 2.80 3.10 3.65 4.00 4.55 4.80 5.05 2.84 0.73 1.00 1.30 1.60 2.10 2.45 2.70 3.00 3.45 3.90 4.40 4.70 4.85 3.15 0.65 0.90 1.10 1.40 1.90 2.20 2.40 2.70 3.10 3.60 4.00 4.25 4.55 3.45 0.70 0.90 1.10 1.40 1.80 2.10 2.30 2.60 2.95 3.30 3.70 3.95 4.15 3.76 - 0.70 0.90 1.00 1.55 1.75 1.95 2.10 2.45 2.85 3.30 3.50 3.75 4.06 - 0.80 1.00 1.20 1.60 1.75 1.95 2.10 2.45 2.75 3.10 3.30 3.45 4.36 - - 0.80 0.95 1.20 1.40 1.50 1.75 2.00 2.25 2.50 2.70 2.80 4.66 - - 0.70 0.80 1.00 1.20 1.30 1.40 1.70 1.90 2.05 2.20 2.35 4.96 - - - 0.80 1.00 1.15 1.30 1.40 1.60 1.80 2.00 2.10 2.30 5.55 - - - 0.65 0.80 0.90 1.00 1.10 1.30 1.50 1.75 1.90 2.00 6.14 - - - - 0.65 0.75 0.85 0.95 1.15 1.40 1.60 1.80 1.90 7.3 - - - - - - - - - - - - 0
  • 21. Result and discussion Fig. 3. Antifungal effects of cycle 1 extraction liquid from different concentration (white rot fungi)
  • 22. Result and discussion Fig. 4. Antifungal effects of cycle 1 extraction liquid from different concentration brown rot fungi)
  • 23. Result and discussion 100 90 80 Anti fungal index (%) 70 60 50 TV 40 GT 30 20 10 0 1.92 2.53 2.84 3.15 3.45 3.76 4.06 4.36 4.66 4.96 5.55 6.14 7.30 9.55 11.72 Copper concentration in medium (mg L-1) Fig. 5. Plots of antifungal index (AI) versus copper concentration
  • 24. Summary  Acid extraction microwave treatment is a fast and effective method to remove Cu, Cr and As from CCA-treated waste wood.  Soaking solution has the potential to continue remove Cu, Cr and As from CCA-treated waste wood.  Soaking solution showed the antifungal activities against white-rot and brown-rot fungi.