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Phytoremediation: What Every Good Chemical Engineer Should Know. Steven C. McCutcheon, Ph.D., P.E., D.WRE Past President American Ecological Engineering Society Director, Region 5, American Society of Civil Engineers Faculty of Engineering, University of Georgia. Acknowledgements.

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phytoremediation what every good chemical engineer should know

Phytoremediation: What Every Good Chemical Engineer Should Know

Steven C. McCutcheon, Ph.D., P.E., D.WRE

Past President American Ecological Engineering Society

Director, Region 5, American Society of Civil Engineers

Faculty of Engineering, University of Georgia

acknowledgements
Acknowledgements
  • Co-editor and coauthors of the book
  • Mike Saunders and students at Georgia Tech
overview
Overview
  • What is phytoremediation?
  • Ecological engineering?
  • Biochemistry has been very, very good to this field

Courtesy Stefan Trapp

phytoremediation
Phytoremediation
  • Use of green plants and other autotrophic organisms to clean up hazardous and other wastes
  • Includes bioremediation by heterotrophic bacteria when plants provide carbon, nutrients, or habitat – rhizodegradation
  • Phytoextraction – accumulates metals in aboveground tissues for harvest
  • Phytodegradation or transformation
  • Phytocontainment and stabilization
  • Phytovolatilization and other types
history of phytoremediation
History of Phytoremediation
  • Raskin coined the term in a 1991 proposal funded by U.S. EPA Superfund Program on metals accumulation
  • Cunningham and Berti (1993) first used the term in the open literature
  • Schnoor et al. (1995) first expanded the term in the open literature to include transformation of organics
strengths and limitations
Solar driven, self engineering to ensure nutrients/water

Aesthetically

pleasing, eco-restoration

Should be cost effective

Shallow depths of soil or water (rooting depths)

Plants mainly transform contaminants

Long durations and large land areas

Strengths and Limitations
ecological engineering
Ecological Engineering:
  • Design of sustainable systems, consistent with self design and other ecological principles, which integrate human society with the natural environment for the benefit of both (Mitsch and Jorgensen, 1989; Mitsch, 1996; Bergen et al., 1997)
self design
Self-Design

The reorganization, substitution and shifting of an ecosystem (dynamics and functional processes) whereby it adapts to the environment superimposed upon it.

(Mitsch, Jorgensen)

some areas of ecological engineering
Some Areas of Ecological Engineering
  • Wetland Restoration and Creation
    • Ecohydrology
  • Wetland Wastewater Treatment
  • Bioremediation, Phytoremediation, and Mycoremediation
  • Bioengineering
    • Stream bank stabilization
    • Slope stabilization
  • Stream and River Corridor Restoration and Engineering
    • Riparian buffer designation and design
    • Wetland design to control runoff
    • Floodplain/Hyporheic Zone Management
  • Carrying Capacity Studies
  • Green Space Engineering
parrot feather myriophyllum aquaticum

Observation of self-engineering: Alabama Army Ammunition Plant, Childersburg

  • Widespread TNT contamination 1960s to 1980s
  • Beaver dams led to parrot feather and clean water and sediment
  • Pine and grasses encroached on sterile bare soils to reduce TNT concentrations
Parrot feather (Myriophyllum aquaticum)
laboratory and pilots
Laboratory and Pilots
  • Plants protect enzymes and rapidly transform TNT and other explosives
  • Dead plants maintain activity for weeks to allow new plants to colonize
  • Crude enzyme extracts rapidly deactivated by proteases and metals
populus spp
Populus spp.
  • Release of sugars and other simple exudates controls redox
  • Reducing conditions favors microbial dehalogenation
  • Evapotranspiration can halt ground water plume migration and pull contaminated water into vadose zone
  • Contaminants taken into the trees are mineralized
slide13

Potential Savings if the Promise of Phytoremediation is Proven

  • $0.25 to 0.5 billion at ammunition sites
  • $1 to $2 billion for solvent plumes

$1 trillion

slide15

Species

Contaminant

Populusspp. (poplar, cottonwood)

Hydrocarbons, chlorinat. solvents, explosives, MTBE, HCN, wastewater, & pesticides

Salix spp. (willow)

Hydrocarbons, HCN wastewater, leachate

Ecalyptus spp., Tamarix

Hydraulic control, arsenic

Acer rubrum (red maple)

Landfill leachate

Pinus radiata, (Monterey pine)

Municipal wastewater

Morus rubra (red mulberry)

PAHs

Thespesia populnea (milo) and Prosopis pallida (kiawe)

Petroleum hydrocarbons

general advances

IA IIA IIIA IVA VA VIA VIIA O

1

H+

H

7.8

1.0079

Suitable for wetland treat-ment

Suit-able for phyto-extrac-tion

KEYS

Figure 1-1

Periodic Table of Elements Suitable for Phytoremediation

2

He

4.0026

3

Li+

LI

6.941

4

BeOH+

Be

9.012

Atomic number

Species in freshwaters

Symbol

pConc. in US Rivers (-log M)

Atomic Mass

5

B

10.81

6

HCO3-

C

2.7

12.011

7

NO

N

4.5

14.007

8

O2

O

3.5

15.9994

9

F-

F

5.3

18.9984

10

Ne

20.179

11

Na+

Na

3.1

22.990

12

Mg2+

Mg

3.3

24.31

IIIBIVBVB VIB VIIB VIIIBIB IIB

13

Al(OH)3

Al

6.0

26.98

14

H4SiO4

Si

4.5

28.09

15

HPO

P

5.4

30.974

16

SO42-

S

3.4

32.064

17

Cl-

Cl

3.4

35.453

18

Ar

39.948

19

K+

K

4.1

39.102

20

Ca2+

Ca

3.0

40.08

21

Sc

44.96

22

Ti

47.90

24

Cr6+,3+

Cr

6.7

52.00

25

Mn4+,2+

Mn

6.4

54.94

26

Fe3+,2+

Fe

6.0

55.85

27

Co2+

Co

58.93

28

Ni2+

Ni

7.3

58.71

29

Cu2+,+

Cu

7.0

63.546

30

Zn2+

Zn

6.6

65.38

31

Ga

69.72

32

Ge

72.59

33

HAsO

As

7.9

74.92

34

SeO

Se

8.6

78.96

35

Br-

Br

5.9

79.904

36

Kr

83.80

37

Rb

85.47

38

Sr2+

Sr

87.62

39

Y

88.91

40

Zr

91.22

41

Nb

92.91

42

Mo

95.94

43

Tc

98.91

44

Ru

101.07

45

Rh

102.91

46

Pd

106.4

47

Ag

107.868

48

Cd2+

Cd

8.1

112.4

49

In

114.82

50

Sn2+

Sn

118.69

51

Sb

121.75

52

Te

127.60

53

I-,IO

I

126.90

54

Xe

131.30

55

Cs+

Cs

132.91

56

Ba2+

Ba

6.0

137.34

57

La

138.91

72

Hf

178.49

73

Ta

180.95

74

W

183.85

75

Re

186.2

76

Os

190.2

77

Ir

192.2

78

Pt

195.09

79

Au

196.97

80

Hg(OH)2,+

Hg

8.0

200.59

81

Tl

204.37

83

Bi

206.96

84

Po

(209)

85

At

(210)

86

Rn

(222)

87

Fr

(223)

88

Ra

226.0

89

Ac

(227)

92

+3,4,6

U

238

23

V

50.94

82

Pb2+,Pb+

Pb

7.7

207.20

General Advances
  • “Green liver model” -- enzymology and proteomics more mammalian than microbial
    • Oxidation or hydroxylation
    • Conjugation
    • Segregation, binding or excretion
  • Xenobiotic chemicals usually treatable if there is an analog among the spectrum of natural biomolecules
  • Transgenic plants possible and necessary for any unique molecules created by humankind
  • Tip of the iceberg of activities of plant proteins
  • Tolerance—insights from medicine and mammalian biochemistry
  • Rooting at depth & exploration of soil to clean up
  • Stand level transpiration  trees as solar pumps using ground water models to design

Transition Elements

better living through biochemistry tph pah pcb et al
Better Living through biochemistry: TPH, PAH, PCB, et al.
  • Aseptic tissue cultures to screen for plant v. microbial metabolism
  • Ecology of plant-microbe interactions
  • Grass rooting and hydrocarbon degradation (proof of concept)
  • Seeking proof of principle at numerous sites worldwide
explosives
Explosives
  • Extensive axenic tissue cultures to map transformation of TNT
  • Kinetics of transformation for wetland design – state of the practice
  • IA Army Ammunition Plant, successful wetland application
elisa for field testing and characterization
ELISA for Field Testing and Characterization

Courtesy of George Bailey, ERD, NERL, ORD, US EPA

transcriptional profiling arabidopsis thaliana root responses to explosives
Transcriptional Profiling: Arabidopsis Thaliana Root Responses to Explosives

SAGE—Serial Analysis of Gene Expression—30 000 tags

Very different metabolism

RDX

(Hexahydro-1,3,5-trinitro-1,3,5-triazine)

TNT

(Trinitrotoluene)

putative glutathione transferase

NPR1-like protein

MYB like protein

DnaJ-like protein

Detoxification reactions that follow the green liver model of Sandermann

carbamoyl phosphate synthetase small subunit

gamma-VPE (vacuolar processing enzyme)

transporter-like protein

putative transcription factor

putative serine/threonine-protein kinase

putative peroxidase

monodehydroascorbate reductase - like protein

putative 3-dehydroquinate synthase

vacuolar H+-ATPase subunit H (VHA-H)

NAM, no apical meristem, - like protein

unknown function; similar to bacterial tolB proteins

vacuolar H+-transporting ATPase 16K chain P2

putative transcription factor

alpha-hydroxynitrile lyase-like protein

cytochrome P450, putative

(TCCCCTATTA) no matches in genome

chlorinated solvents
Chlorinated solvents
  • Biochemistry of TCE phytodegradation in terrestrial and wetland plants
  • Fate of TCE in indigenous vegetation
  • Demo– Control/treatment of plume
  • 5-y pilot, TCE Plume treatment/control
  • Ground water modeling to design tree plantations to control and treat solvent plumes
tip of mother nature s bio iceberg
Tip of Mother Nature’s Bio-Iceberg
  • Identified approximately 100 enzymes involved in xenobiotic metabolism
  • Yet vascular plants seem to have at least 25000 genes that produce one or more biomolecules
  • Genomes of each species are diverse:
    • Arabidopsisthaliana—25 000 genes
    • Pinus taeda—110 000 genes
    • Maize, wheat, rice—25 000 to 40 000 genes
  • Native Australian flora even more diverse: millions of years of isolated evolution under stressful climatic conditions
    • Very unique biomolecules—most dangerous poisons on the planet that must be metabolized by some organism or environmental process
    • Should be extensive overlap with pharmaceutical and nutraceutical investigations
slide30

Figure 3-1

Increased human and ecological risk

Increased genetic engineering

Transgenic plants

Cultivated plants

Maintained indigenous plants

Sustainable native or indigenous organisms

Sustainable native or indigenous organisms

Maintained indigenous plants

Cultivated plants

Transgenic plants

Increased maintenance, monitoring,

and control required

Increased residual disposal

need for transgenic plants
Need for Transgenic Plants
  • Humankind has been more inventive of xenobiotics than the natural metabolism is capable of handling
  • Both metabolic and genetic engineering will be necessary to sustainably handle all the man-made chemicals possible
  • Feasibility has been proven:
    • Hg and As volatilization by transgenic Arabidopsis thaliana but there are stability problems in trees
    • Transgenic tobacco with human genes for cytochrome P450 1E1 to better metabolize trichloroethylene
    • Transgenic plants for explosives and nitroaromatics
better living through plant biochemistry
Better Living through Plant Biochemistry
  • Sustainable recycling of some organic contaminants
  • Some plant metabolism faster, but several years and large land areas required
  • Metals accumulation in plants helps restore ecosystems inexpensively but takes time and residuals are a problem
  • Solar driven, usually inexpensive, but lacks process control