張書奇教授分享專題_底泥整治技術應用現況與發展趨勢

張書奇
國立中興大學環境工程學系副教授兼系主任
Shu-Chi Chang, Ph.D., P.E., P.A.
Associate Professor and Chair
Department of Environmental Engineering
National Chung Hsing University
1
108年12月3日(星期二)
於成大會館(臺南市東區大學路2號) 3樓會議廳

大綱
底泥組成與底泥污染
底泥污染整治技術
應用現況
發展趨勢

底泥組成
(Mulligan et al., 2010)
Primary minerals
Sediment
Dredged material
Fulvic acid
Humic acidCrystalline
Inorganic Organic Fresh water CO2, H2S,
CH4, etc.
Pore waterSoil particle Gas
Non-crystalline
Allophane, etc.
Sea water
Dissolved compds
Humins, lignins, etc.
Peptides, lipids, carbohydrates
3

底泥污染物
 Contaminants
 Heavy metals
 Organic pollutants
 Grease and oils
 PAHs
 PCBs
 PBDEs
 BPA
 Phthalates
 Chlorobenzenes
 Dioxin and furans
 Herbicides and pesticides
 etc.
 Emerging contaminants
NAPL= non-aqueous phase liquid
5

污染物特性
 Molecular weight
 Density
 Water solubility
 Kow
 Koc
 KH
 Vapor pressure
 Viscosity
 Biodegradability
 others
6

污染物比較
Congeners
MW
（g/mole）
log Kow
Vapor pressure
（Pa, 25C）
Water solubility
（g/L）
BaP 252.3 6.04 7.0×10-7 3.8
HCB 284.8 5.73 1.45×10-3
6
Aroclor 1254 328 6.5 1.03×10-2
12-57
PentaBDE 564.8 6.5-7.0 4.69×10-5 13.3
OctaBDE 801.5 8.4-8.9 6.59×10-6 <1
DecaBDE 959.2 10.0 4.63x10-6 <0.1
Compounds MW（g/mole） Log Kow
Vapor pressure
（Pa）
Water solubility
（g/L）
1,2-DCA 99 1.47 1.09E+04 8,500,000
CA 64.5 1.43 1.60E+04 5,700,000
TCE 131.4 2.53 9.84E+03 1,100,000
cis-DCE 96.9 1.86 2.70E+04 3,500,000
trans-DCE 96.9 1.93 4.43E+04 6,260,000
1,1-DCE 96.9 2.13 8.03E+04 3,344,000
VC 62.5 1.38 3.54E+05 2,763,000 7

張書奇
8

整治技術
 Physical: separation, rinsing, floatation, ultrasonic
 Chemical/thermal treatment: oxidation,
electrokinetic, solidification, vitrification, thermal
desorption
 Biological: Slurry reactor, land farming,
compositing, bioleaching, biotransformation,
phytoremediation
 Integrated technology: capping (active capping),
ISPIE-BiRD, monitored natural recovery
9

主要技術
(Adriaens et al., 2006)
10

疏濬法 Dredging
(Palermo et al, 2008)
11

疏濬物處理
(Mulligan et al., 2010) 12

限制之最終處置 Confined disposal
(Netzband, 2002) 13

限止之水域處置 Contained
aquatic disposal
(Thomas and Concord, 2005) 14

固化法
 水泥固化：加入水泥塑型
 加藥固化：瀝青化、聚合化(PE射出成形)
 加熱固化
 玻璃化
 電漿玻璃化
 焦耳熱玻璃化
 電磁感應玻璃化

加蓋法 Capping
(Aldrich, 2010)
17

主動加蓋或混合加蓋
Active capping or mixing
 Organic clay (Lintern et al., 2015)
 Activated carbon (Beckingham and Ghosh, 2011)
 Ash (Burgess et al., 2009)
 Apatite (Peng et al., 2009)
 Reactive mat (De Gisi et al., 2017)
 Biochar (Wang et al., 2018)
18

植生復育 Pytoremediation
 Phytoextraction
 Rhizofiltration
 Phytodegradation
 Hydraulic control
 Phytovolatization
 Rhizoremediation
 Phytostabilization

生物刺激 Biostimulation
 encouraging the indigenous microbial population to
degrade contaminants by influencing the factors
which enhace microbial growth.
 加入主要營養份：如Ｃ、Ｎ、Ｐ、Ｓ、K、Mg、Ca、
Na等
 加入微量元素及生長因子
 加入刺激因子(?)

生物擴增 Bioaugmentation
 加入已知具有降解能力之菌群
 通常是加入外來菌群
 其結果有時不是完全靠加入之菌
群繼續大量生存所導致之較佳降
解，而有可能是現地菌群與外來
菌群衍生出新基因型生物（new
genotype)(Lendvay et al.,
2003)
 有時仍需加入適合此菌群生長之
營養成分

生物群聚再造 Bioreengineering
 未加入任何外來菌群，只是利用環境條件來調整菌相，
可導致現地菌群之群聚再造 (microbial community re-
engineering)
 如利用熱篩即為其中一種方式(Chang et al., 2019a;
Chang et al., 2019b)
微生物培養基質
三氯乙烯
濃度
Normalized
MSTDR*, k
Dehalococcoides
mccartyi strains 11a
DCB-1 medium 72-85 mg/L 11.5X**
KB-1TM/VC mixed culture
Modified yeast
extract medium
11 mg/L 1X**
NCHU mixed culture
Yeast extract
medium
1.0-16 mg/L 256X**

Monitored natural recovery
(MNR)
23

MNR
24

Management
Suspended solids
(Mulligan et al., 2010) 25

張書奇
26

in situ phase inversion emulsification
and biological reductive dechlorination

創新亮點
(1) Hot water-in-oil (W/O) emulsion injection to enhance
HOCs desorption from sediment organic matter and
partition in oil
(2) Holding for a short period of time to encourage
desorption and mass transfer of HOCs and simultaneous
heat selection of microorganisms
(3) Cool water injection to induce phase inversion to form an
oil-in-water (O/W) emulsion with much smaller HOC-
rich oil droplets in water, which could be easily displaced
by incoming water
(4) Accelerated biological reductive dechlorination using
residual emulsion ingredients and HOCs as electron
donors and acceptors

相反轉乳化
Phase inversion emulsification
Fernandez, P., André, V., Rieger, J., Kühnle, A., 2004. Nano-emulsion formation by emulsion phase inversion.
Colloids and Surfaces A: Physicochemical and Engineering Aspects 251, 53-58.

脫附Desorption tk
slow
tk
rap
t slowrap
eFeF
S
S 

0
kslow (h-1) for HCB and selected PCBs at 60 °C was about 40 to 92 times larger than
those at 20 °C. Thus, at 80 °C, the kslow could be even larger and this is why the removal
is much better than those tested at room temperature by using similar emulsion
formulation.
Cornelissen, G., van Noort, P.C.M., Parsons, J.R., Govers, H.A.J., 1997. Temperature Dependence of Slow Adsorption and
Desorption Kinetics of Organic Compounds in Sediments. Environmental Science & Technology 31, 454-460.

溶解
 log Kow of HCB decreases from 5.46 to 5.17 as
temperature increased from 25 °C to 45 °C with a slope
of d(log Kow)/dT = -0.0144.
Bahadur, N.P., Shiu, W.-Y., Boocock, D.G.B., Mackay, D., 1997. Temperature dependence of octanol−water
partition coefficient for selected chlorobenzenes. Journal of Chemical & Engineering Data 42, 685-688.

熱篩
Nissilä, M.E., Tähti, H.P., Rintala, J.A., Puhakka, J.A., 2011. Effects of heat treatment on hydrogen production potential and
microbial community of thermophilic compost enrichment cultures. Bioresource Technology 102, 4501-4506.

最適溫度區間
 For most anaerobes capable of reductive
dechlorination, the range is around 30-37°C

管柱試驗- ISPIE
0
2
4
6
8
10
12
Upper Middle Lower
Arclor1254,mg/kg
Sediment core section
Before
After
0
2
4
6
8
10
12
Upper Middle LowerHCB,mg/kg
Sediment core section
Before
After

脫氯進行式
0
20000
40000
60000
80000
100000
120000
140000
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61 63 65 67 69 71 73 75 77 79 81 83 85 87 89 91 93 95 97 99 101 103 105 107 109
Peakarea
Peak number
day 0
day 14
day 49

底泥整治模場試驗
 二仁溪模場試驗
 PAHs
 PCBs
 Dioxins
 重金屬
4-13
38

模場試驗組合
簡寫添加否? ISPIE 加營養劑? 加微生物?
WBK No No No No
WNR No Yes No No
WBS No Yes Yes No
WBA No Yes Yes Yes
FBK Yes No No No
FNR Yes Yes No No
FBS Yes Yes Yes No
FBA Yes Yes Yes Yes
40

總移除率
41新增頁尾
0%
20%
40%
60%
80%
100%
120%
WBK WNR WBS WBA
Overallremoval
Test conditions
Upper
Lower
Mean
Aroclor 1254 HCB

Benchmarking
Pollutants Time (weeks)
Experimental
setup Removal References
2,3,4,5,6-
pentachlorobiphenyl
12
Lab batch study /
Fresh
~85%* Natarajan et al., 1998
Aroclor 1254 8
Lab batch study /
Fresh
< 63%** Quensen et al., 1990
2,3,5,6-CB; 2,3,4,5-
CB;2,3,4,5,6-CB
10
Lab batch study /
Fresh
100% for 2,3,4,5-CB*
100% for 2,3,4,5,6-
CB*
60-80% for 2,3,5,6-
CB*
Chang et al., 2001
Aroclor 1254 50
Lab batch study /
Fresh
58~63% for meta-
and para-Cl*
no apparent removal
of ortho-Cl*
Pakdeesusuk et al.,
2003
Aroclor 1254 17
Lab batch study /
Fresh
25%** Kaya et al, 2018
HCB 20
Lab batch study /
Fresh
47.6% - 59.4%* Hirano et al., 2007
HCB 5
Lab batch study /
Fresh
100%* Zhou et al. 2015
Weathered Aroclor
1254 and HCB
10
Field microcosm
/Weathered
98%* This study
Notes * means the removal is based on the disappearance of target compounds. ** means the removal is based on chlorine removal. 42

NGS
優勢菌
432019年11月30日新增頁尾

Phylogenetic classification of
NGS data
No. NRL NRU BKL BKU slope R2 kingdom phylum class order
1 3.5% 4.7% 1.1% 2.6% 1641 0.7515 Archaea Euryarchaeota Methanomicrobia
Methanosarcinal
es
2 1.7% 1.3% 1.7% 1.6% -6840 0.2238 Bacteria Chloroflexi ― ―
3 1.4% 0.9% 1.5% 1.5% -5779 0.4378 Bacteria Proteobacteria
Epsilonproteobacter
ia
Campylobacteral
es
4 1.2% 0.9% 1.3% 1.7% -6711 0.5395 Bacteria Proteobacteria Deltaproteobacteria Desulfobacterales
5 0.7% 1.9% 1.2% 0.9% 1406 0.0763 Bacteria Firmicutes Clostridia Clostridiales
6 0.9% 0.9% 1.1% 1.3% -12709 0.8448 Bacteria Chloroflexi Anaerolineae Anaerolineales
7 0.9% 0.8% 0.9% 1.5% -6058 0.4391 Bacteria Chloroflexi Dehalococcoidia MSBL5
8 0.5% 1.8% 0.6% 0.5% 2228 0.2636 Bacteria Firmicutes Clostridia Clostridiales
9 0.8% 0.7% 0.8% 1.0% -15890 0.5666 Bacteria Actinobacteria Acidimicrobiia Acidimicrobiales
10 1.3% 0.8% 0.4% 0.7% 5750 0.6114 Archaea Euryarchaeota Methanomicrobia
Methanosarcinal
es
11 1.2% 0.7% 0.6% 0.7% 7077 0.4712 Archaea Bathyarchaeota ― ―
12 2.4% 0.2% 0.1% 0.1% 1571 0.4002 Bacteria Proteobacteria
Gammaproteobacte
ria
Oceanospirillales
442019年11月30日新增頁尾

模場試驗結論
 在現地模場試驗，單一次的ISPIE操作可去除約60%風
化之多氯聯苯及六氯苯
 對風化之六氯苯及多氯聯苯，在70天內，總去除率可
達98%。
 與以往研究不同，耐熱之古細菌Methanosaeta spp.,
可能是此菌群中最重要之多氯聯苯與六氯苯降解菌。
 此結果顯示，微生物群聚再造 (Bioreengineering or
microbial community reengineering)可能是一極佳
之生物整治技術。
45

發展趨勢
 技術走勢
 現地技術In situ technology
 無擾動或是低度擾動No or low disturbance
 快速降解或無毒化(to finish the project within
a 6-month dry season)
 無衍生之負面效應No derived negative impact
 低成本或是高效率Low cost or more effective
 整治技術之綠色永續整治評價
 固化法應依循環經濟思維再優化
 資源化之新資材建議以低毛利率之大宗貨物較為
可行
46

結論
 底泥具有豐富之生態且是人類食物網絡重要一環，需
要審慎保護。
 底泥中有機污染物多為POPs，因輸水特性而不易隨水
流移動且欠缺生物可及性，不易生物降解，而具有持
久污染特性。
 底泥中重金屬容易與硫化物形成錯化物而長期蓄積，
不易釋放至水中。
 屬於生物重整 (Bio-reengineering)之ISPIE-BiRD
可能可以有效整治有機物污染之底泥場址。
 未來之底泥技術研發均應將GSR納入考量。
47

誌謝
 行政院環境保護署土壤及地下水污染整治基金管理會
之「土壤及地下水污染整治基金補助研究與模場試驗
專案」之研究經費補助。
 水利署第六河川局核發河川地使用許可。
 模場所在地主管機關台南市政府核准二仁溪模場試驗
計畫。
 科技部計畫NSC 98-2622-E-005-024-CC2之經費補
助
48

張書奇教授分享專題_底泥整治技術應用現況與發展趨勢

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