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21 November 2008 Biogeochemical cycling of Biogeochemical cycling of arsenic in sedimentary basin of arsenic in sedimentary basin of southwestern Taiwan southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering National Taiwan University
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Page 1: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

21 November 2008

Biogeochemical cycling ofBiogeochemical cycling ofarsenic in sedimentary basin ofarsenic in sedimentary basin of

southwestern Taiwansouthwestern Taiwan Wang, Sheng Wei

Department of Bioenvironmental Systems Engineering

National Taiwan University

Page 2: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Introduction

Arsenic is carcinogenic, and can cause other human health effects

As(III), inorganic species in anaerobic environment, is generally considered more mobility and toxic than As(V), the primary form in aerobic environment

Most frequently found in groundwater As released from natural sources to groundwater is

the dominant cause

Page 3: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Introduction

As contamination in groundwater of the world As contamination in groundwater of the world

Page 4: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Introduction

As in Bangladesh As in Bangladesh

Page 5: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

C h o u sh u i r iv e r

Ta i

wan

Str

a it

Cen

tra l

Mou

n ta i

n

3

2 175

2 98 1 31 1 73 22 39 3 7

3 02 62

3 63 51 91 56

3 9

2 8

2 4

2 21 4

4 4 03 4

4 13 83 32 71 8

1 61 011

3 12 52 01 2

1

23 4

56

789

1 0

111 21 31 41 5

1 6

1 7 1 8

1 92 0 2 1

2 22 3

2 4 2 52 6 2 7

2 82 9 3 0

3 13 23 3

0 1 0 2 0 k m

S ou th ern C h ou sh u i r iver a llu v ia l fan

C h ian an p la in

P e ik an g riv e r

P ach an g r iv e r

T sen g w en riv e r

E rn jen r iv e r

T a iw a n

Introduction

High As in deep wells of depth 60-300m has been proved to

be associated with blackfoot

disease of the Chianan plain

High As in shallow wells of

depth 30-40m have been found in the southern Choushui river alluvial fan (Yun-Lin county)

Page 6: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Aquaculture water

High As content groundwater

Effect human health

Sediment

Food

Fish/ShellfishBioaccumulation

Ingestion

Aquaculture Ecosystem

Drinking

As

As As

Introduction

Exposure pathway of As in southwest TaiwanExposure pathway of As in southwest Taiwan

Page 7: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

-350

-300

-250

-200

-150

-100

-50

0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

As (mg/L)D

epth

(m

)

-300

-250

-200

-150

-100

-50

0

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

As (mg/L)

Dep

th (

m)

High As

High As

High As

High As

Chianan plain Chianan plain

Choushui river alluvial fan Choushui river alluvial fan

The vertical distribution of As in groundwater in Taiwan The vertical distribution of As in groundwater in Taiwan

Page 8: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Study areasC h o u sh u i r iv e r

Ta i

wan

Str

a it

Cen

tra l

Mou

n ta i

n

3

2 175

2 98 1 31 1 73 22 39 3 7

3 02 62

3 63 51 91 56

3 9

2 8

2 4

2 21 4

4 4 03 4

4 13 83 32 71 8

1 61 011

3 12 52 01 2

1

23 4

56

789

1 0

111 21 31 41 5

1 6

1 7 1 8

1 92 0 2 1

2 22 3

2 4 2 52 6 2 7

2 82 9 3 0

3 13 23 3

0 1 0 2 0 k m

S o u th ern C h o u sh u i r iv er a llu v ia l fa n

C h ia n a n p la in

P e ik an g riv e r

P ach an g riv e r

T sen g w en riv e r

E rn jen r iv e r

A A '

B

B '

The southern Choushui

river alluvial fan 41 hydrological stations 107 monitoring wells

The Chianan plain 33 hydrological stations 100 monitoring wells

Page 9: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Chianan plain

Chianan plain

Choushui river alluvial fan

Choushui river alluvial fan

Hydrogeological profile

Hydrogeological profile

Study areas

Page 10: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Topic

11Where is the As in ground water from ?Where is the As in ground water from ?

33Have the As problemsalready been solved ? Have the As problemsalready been solved ?

22How dose the As releaseinto groundwater ?How dose the As releaseinto groundwater ?

Characterization of groundwater quality

Composition of sedimentary deposits

Page 11: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Characterization of groundwater quality

Taiwan Sugar Company (2003; 2004) As concentrations of groundwater

0.12±0.14 mg/L in the southern Choushui river alluvial fan

0.30±0.35 mg/L in the Chianan plain

Monitoring wells of that As > 0.01 mg/L 70% in the southern Choushui river alluvial fan> 95% in the Chianan plain

Page 12: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Factor analysis Liu et al. (2003): The Choushui river alluvial fan 33 hydrological stations, 100 monitoring wells of the Chianan

plain 3 layers: 0-70m, 70-170m, and >170m EC, Eh, pH, TDS, Alk, TOC, NH4

+, SO42-, Cl-, Ca2+, Mg2+, Na+,

K+, As, Fe

Characterization of groundwater quality

Page 13: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Factor analysis

Factor EigenvaluePercentageof variance

Cumulative percentageof variance

1 7.55 50.34 50.34

2 2.79 18.62 68.96

3 1.28 8.56 77.52

4 0.79 5.24 82.75

5 0.68 4.51 87.27

6 0.48 3.18 90.45

7 0.42 2.77 93.22

8 0.31 2.08 95.30

9 0.27 1.83 97.12

10 0.20 1.33 98.45

11 0.12 0.80 99.25

12 0.08 0.52 99.76

13 0.03 0.17 99.93

14 0.01 0.04 99.98

15 0.00 0.02 100.00

Page 14: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Variable Factor 1 Factor 2 Factor 3

EC 0.85 0.02 0.14

Eh -0.42 -0.67 0.15

pH -0.09 0.37 -0.79

TDS 0.98 0.02 0.09

Alk -0.14 0.82 -0.07

SO42- 0.89 -0.12 -0.05

Cl- 0.97 0.04 0.13

Ca2+ 0.79 -0.18 0.23

Mg2+ 0.93 -0.12 0.01

Na+ 0.97 0.05 0.10

K+ 0.95 -0.06 0.02

As -0.19 0.68 0.07

Fe 0.18 0.40 0.72

TOC 0.00 0.91 0.09

NH4+ 0.61 0.18 0.38

Loadings for three-factors Loadings for three-factors

As enrichment factorAs enrichment factorSalinization factorSalinization factor

Factor analysis

Page 15: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Redox zoning

Redox zoning Chen and Liu (2003): The Choushui river alluvial fan Definition of redox zones were same with Chen and Liu (2003) zone 1: Eh >0, and DO or NO3

->0.5 mg/L

zone 2: Eh <0, and with detectable dissolved sulfide zone 3: Eh <0, and without detectable dissolved sulfide

Page 16: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Redox zoning

1 5 0 0 0 0 1 6 0 0 0 0 1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 02 5 3 0 0 0 0

2 5 4 0 0 0 0

2 5 5 0 0 0 0

2 5 6 0 0 0 0

2 5 7 0 0 0 0

2 5 8 0 0 0 0

2 5 9 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

1

234 5

7891 0 111 2

1 3 1 41 5

1 6 1 7

1 8 1 9 2 02 1

2 22 3

2 42 52 6 2 7

2 8 2 93 0

3 1

3 2

1 5 0 0 0 0 1 6 0 0 0 0 1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 02 5 3 0 0 0 0

2 5 4 0 0 0 0

2 5 5 0 0 0 0

2 5 6 0 0 0 0

2 5 7 0 0 0 0

2 5 8 0 0 0 0

2 5 9 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

3 3

3 1

3 0 2 92 8

2 7 2 5

2 3 2 22 1

2 01 9

1 61 5

1 411

9 8 7

64 3

1

1 5 0 0 0 0 1 6 0 0 0 0 1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 02 5 3 0 0 0 0

2 5 4 0 0 0 0

2 5 5 0 0 0 0

2 5 6 0 0 0 0

2 5 7 0 0 0 0

2 5 8 0 0 0 0

2 5 9 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

1

4 5

891 0 111 2

1 31 5

1 6 1 7

1 8 1 9 2 02 1

2 22 3

2 5

2 8 2 93 0

3 23 3

1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 0 2 1 0 0 0 0 2 2 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

2 6 2 0 0 0 0

2 6 3 0 0 0 0

2 6 4 0 0 0 0

2 6 5 0 0 0 0

2 6 6 0 0 0 0

2 6 7 0 0 0 0

3

2 175

2 98 1 31 1 73 22 39 3 7

3 02 62

3 63 51 91 56

3 9

2 8

2 4

2 21 4

4 4 03 4

4 13 83 32 7

1 8

1 61 011

3 12 52 01 2

1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 0 2 1 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

2 6 2 0 0 0 0

2 6 3 0 0 0 0

2 6 4 0 0 0 0

2 6 5 0 0 0 0

2 6 6 0 0 0 0

2 6 7 0 0 0 0

3

2 175

2 98 1 31 1 73 22 39 3 7

3 02 62

3 63 51 91 56

3 9

2 8

2 4

2 21 4

4 4 03 4

4 13 83 32 7

1 8

1 61 011

3 12 52 01 2

1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 0 2 1 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

2 6 2 0 0 0 0

2 6 3 0 0 0 0

2 6 4 0 0 0 0

2 6 5 0 0 0 0

2 6 6 0 0 0 0

2 6 7 0 0 0 0

3

2 175

2 98 1 31 1 73 22 39 3 7

3 02 62

3 63 51 91 56

3 9

2 8

2 4

2 21 4

4 4 03 4

4 13 83 32 7

1 8

1 61 011

3 12 52 01 2

0-70 m 70-170 m >170 m

Zone 1

Zone 2

Zone 3

Distribution of redox zones at different depths Distribution of redox zones at different depths

Zone 1 Eh >0 DO or NO3

->0.5 mg/LZone 2 Eh <0 with sulfideZone 3 Eh <0 without sulfide

Aquifer 1 Aquifer 3Aquifer 2

Page 17: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Composition of sedimentary deposits

13 drilling stations 655 samples

3 m intervals, <100m 10 m intervals, >100m

Analysis AAS+HG

11

32

1

5

1012

7

9

13

6 8

4

0 1 0 2 0 3 0

C h o u sh u i R iv e r

P e ik ang R iv e r

Tai

wan

Str

a it

Cen

tra l

Mou

n ta i

n

Y u n -L in co u n ty

T a iw a n

k m

Page 18: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Composition of sedimentary deposits

As distribution of core samples

As distribution of core samples

Log-normaldistribution

Log-normaldistribution

Geometric mean: 2.27±1.43 mg/kg

Max: 590 mg/kg

Page 19: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0-3 0 0

-2 5 0

-2 0 0

-1 5 0

-1 0 0

-5 0

0

Dep

th(m

)

-0 .2

0 .7 5

0 .8 6

6 7 8 9 1 0 11 1 2 1 3

lo g (A s(m g /k g ))

D is tan ce (x 1 0 0 m )

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0

D is tan ce (x 5 0 m )

-3 0 0

-2 5 0

-2 0 0

-1 5 0

-1 0 0

-5 0

0

Dep

th(m

)

-0 .2

0 .7 5

0 .8 6

lo g (A s(m g /k g ))

1 2 3 4 5 6

Composition of sedimentary deposits

Log CAs(mg/kg) distributions in the west-east and north-south cross section Log CAs(mg/kg) distributions in the west-east and north-south cross section

11

32

1

5

1012

7

9

13

6 8

4

0 1 0 2 0 3 0

C h o u sh u i R iv e r

P e ikang R iv e r

Ta i

wan

Str

a it

Cen

tral

Mou

n tai

n

Y u n -L in co u n ty

T a iw a n

k m

Page 20: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Station Depth (m) As (mg/kg)

1 54 590.00

3 162 117.00

3 180 107.50

8 130 102.60

1 63 76.80

1 6 75.35

10 39 75.08

10 272 74.64

10 152 67.48

11 30 61.88

10 21 56.55

8 12 54.90

1 60 52.35

ShallowShallow

DeepDeep

BothBoth

Tabulate CAs > 50 mg/kg of different drilling stations and depths Tabulate CAs > 50 mg/kg of different drilling stations and depths

Page 21: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

non-marine sequence 1 (<3,000 years B.P.)

marine sequence 1 (3,000-9,000 years B.P.)

non-marine sequence 2 (9,000-35,000 years B.P.)

marine sequence 2 (35,000-50,000 years B.P.)

non-marine sequence 3 (>50,000 years B.P.)

UnknownClaySandGravel

11

32

1

5

1012

7

9

13

6 8

4

0 .0 0 0 1 0 0 0 0 .0 0 0 2 0 0 0 0 .0 0 0 3 0 0 0 0 .0 0 0

C h o u -S h u i R iv e r

Y u n -L in co u n ty

T a iw a n

100 20 30km

Plain view of the marine and non-marine sequences distribution (Huang, 1996)

Plain view of the marine and non-marine sequences distribution (Huang, 1996)

Page 22: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

SandSiltClay

log(

As

Con

cent

rati

on)

3.0

2.5

2.0

1.5

1.0

.5

0.0

-.5

□﹕75% and 25%□﹕50%┬﹕non-outlier Max┴﹕non-outlier Min○﹕outlier 1.5~3 × box*﹕ extremes >3 × box

Composition of sedimentary deposits

Box-plot of log CAs of clay, silt and sand types of core samples Box-plot of log CAs of clay, silt and sand types of core samples

Page 23: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Station Depth (m) Age (year) As (mg/kg)1 108.4 >52000 5.32

3 32.7 2931±81 29.34

3 48.9 8819±99 51.35

3 117.9 43900±1500 13.16

5 157.8 >45000 5.43

6 39.4 3936±64 11.31

7 23.0 5364±89 4.83

7 42.7 8440±90 8.27

7 111.4 39900±1100 110

7 129.6 >50000 1.71

8 91.6 >50000 34.04

9 25.1 7370±100 10.89

9 25.1 7620±80 10.89

9 48.8 9230±60 2.61

9 68.6 36400±500 6.63

9 105.1 >50000 17.22

13 38.2 8330±60 11.51

13 38.8 7920±70 11.51

13 55.0 7090±60 3.37

13 60.0 7850±60 3.01

13 99.0 43300±130 4.61

Geological dating v.s. CAs of core samples Geological dating v.s. CAs of core samples

Page 24: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

R2 = 0.51

0.0

0.5

1.0

1.5

2.0

2.5

-2.0 -1.5 -1.0 -0.5 0.0

log (As) in groundwater (mg/L)

log

(As)

of c

ore

sam

ples

in a

quita

rds

(mg/

kg)

As of core samples in aquitards v.s. As of ground water

As of core samples in aquitards v.s. As of ground water

As of core samples in aquifers v.s. As of ground water

As of core samples in aquifers v.s. As of ground water

R2 = 0.21

0.0

0.5

1.0

1.5

2.0

2.5

-2.0 -1.5 -1.0 -0.5 0.0

log (As) in groundwater (mg/L)

log

(As)

of co

re s

ampl

es in

aqui

fers

(mg/

kg)

Page 25: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Composition of sedimentary deposits

Smedley and Kinniburgh (2002) Extreme As concentrations in natural water are rare, but are most

frequently observed in groundwater

Welch et al. (2000); Nordstrom (2002) Release from natural sources is the dominant cause of elevated As in

groundwater

Edmonds and Francesconi (1997); Francesconi et al. (1998) High As in the marine formation may be attributed to the

bioaccumulation and biotransformation of As in the sea organisms

Page 26: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Topic

22

11Where is the As in ground water from ?Where is the As in ground water from ?

33Have the As problemsalready been solved ? Have the As problemsalready been solved ?

How dose the As releaseinto groundwater ?How dose the As releaseinto groundwater ?

Page 27: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

As release to groundwater

Mandal et al. (1996); Loeppert (1997); Wilkie and Hering (1998) The oxidation of As-bearing pyrite minerals

Nickson et al. (2000); McArthur et al. (2001) Reductive dissolution of As-rich Fe oxy-hydroxides

Acharyya et al. (1999) Competitive exchange of adsorbed As on aquifer minerals with

phosphate ions that migrate into aquifers from the application of

fertilizers to surface soil

Harvey et al. (2002); Smedley and Kinniburgh, (2002) Reductive dissolution of Fe oxy-hydroxides under reducing conditions

is the most probable reason of As accumulation in groundwater

Page 28: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Geochemical modeling

Geochemical calculation: PHREEQC Chemical speciation Saturation index (SI)

SI<0: the potential for dissolution SI>0: the potential for precipitation

3 monitoring wells of 3 layers of the Chianan plain and the southern Choushui river alluvial fan pH, Eh, temperature, DO, Alk, SO4

2-, Cl- , Ca2+, Mg2+, Na+, K+, As, Fe, Mn, NH4

-, NO3- and HS-

Page 29: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Geochemical modeling

1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 0 2 1 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

2 6 2 0 0 0 0

2 6 3 0 0 0 0

2 6 4 0 0 0 0

2 6 5 0 0 0 0

2 6 6 0 0 0 0

2 6 7 0 0 0 0

3 8

2 66

1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 0 2 1 0 0 0 0 2 2 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

2 6 2 0 0 0 0

2 6 3 0 0 0 0

2 6 4 0 0 0 0

2 6 5 0 0 0 0

2 6 6 0 0 0 0

2 6 7 0 0 0 0

4 12 7

6

1 7 0 0 0 0 1 8 0 0 0 0 1 9 0 0 0 0 2 0 0 0 0 0 2 1 0 0 0 0

2 6 0 0 0 0 0

2 6 1 0 0 0 0

2 6 2 0 0 0 0

2 6 3 0 0 0 0

2 6 4 0 0 0 0

2 6 5 0 0 0 0

2 6 6 0 0 0 0

2 6 7 0 0 0 0

4 1

2 3

6

150000 160000 170000 180000 190000 2000002530000

2540000

2550000

2560000

2570000

2580000

2590000

2600000

2610000

1 2

2 1

2 8

150000 160000 170000 180000 190000 2000002530000

2540000

2550000

2560000

2570000

2580000

2590000

2600000

2610000

1 9 2 0

2 7

150000 160000 170000 180000 190000 2000002530000

2540000

2550000

2560000

2570000

2580000

2590000

2600000

2610000

1 6

2 83 0

Page 30: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Geochemical modeling

Chemical species of groundwater in 3 layersChemical species of groundwater in 3 layers

Page 31: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Geochemical modeling

Saturation index of groundwater in 3 layersSaturation index of groundwater in 3 layers

Page 32: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Step Extractant Target phaseMg 1M MgCl2 Ionically bound As

PO4 1M NaH2PO4 Strongly adsorbed As

HCl 1N HCl Coprecipitated with AVS, carbonates, Mn oxide

Ox 0.2M ammonium oxalate/oxalic acid Coprecipitated with amorphous Feoxyhydroxides

Ti 0.05M Ti( )-citrate-EDTA-Ⅲbicarbonate

Coprecipitated with crystalline Feoxyhydroxides

HF 10M HF As oxides and As coprecipitated withsilicates

HNO3 16N HNO3

Coprecipitated with pyrite andamorphous As2S3

hot HNO3 16N HNO3+30% H2O2Orpiment and remaining recalcitrant

As minerals

Sequential extraction

Surface analysesSurface analyses X-ray diffractometer (XRD) X-ray fluorescence (XRF) High resolution x-ray photoelectron spectrometer (HR-XPS)High resolution x-ray photoelectron spectrometer (HR-XPS) Scanning electron microscope (SEM-EDS)Scanning electron microscope (SEM-EDS)

Page 33: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Oremland and Stolz (2003)

Bacteria-mediated mobilization of As into groundwater Bacteria-mediated mobilization of As into groundwater

As release to groundwater

Page 34: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Islam et al. (2004) Reduction of ferric iron took place

before the As release to groundwater The iron-reducing bacteria played a

major role in the subsequent reduction

and release of As The delivery of surface - drived organic

carbon into subsurface communities

may have a dramatic role in As mobility

As release to groundwater

Page 35: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Herbel and Fendorf (2006)

The effects of bacterial processes on arsenic mobilityin iron (hydr)oxide systems

The effects of bacterial processes on arsenic mobilityin iron (hydr)oxide systems

As release to groundwater

Page 36: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Groundwater of YL7 was collected for IRB enrichment Geometric mean of As: 360.57 ppb

C h o u sh u i r iv e r

Y L 7

0 1 0 2 0 k m

S ou th ern C h ou sh u i r iv er a llu v ia l fa n

P e ik an g r iv e r

T a iw a n(R O C )

screen

-25

-5

-10

-15

-20

0

gravalsilty sandclay

As release to groundwater- Batch experiments of IRB

Page 37: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Inject 1 ml groundwater into 10 ml autoclaved IRB

medium H2 or acetate or citrate + Fe3+ → HCO3

- + Fe2+ + H+

Orange →colorless (about 10 days) Transfer 4 times

As release to groundwater- Batch experiments of IRB

Page 38: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Lu (2007) Amorphous Fe (hydr)oxides (HFO) are the primary Fe

mineral and correlate well with the As of core samples 0.5M NaOH was dropwised to 100ml of 0.05M Fe(NO3)3

until pH=7.5-8 HFO reducing experiments (anaerobic condition)

A: HFO+citrate+IRB B: HFO+citrate C: HFO+acetate+IRB D: HFO+acetate

As release to groundwater- Batch experiments of IRB

Page 39: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

As(V) reducing experiments E: As(V)+citrate+IRB F: As(V)+citrate G: As(V)+acetate+IRB H: As(V)+acetate

[As(V)-HFO] reducing experiments I: [As-HFO]+citrate+IRB J: [As-HFO]+citrate K: [As-HFO]+acetate+IRB L: [As-HFO]+acetate

As(III) and As(V) were analyzed by AAS+HG Fe(II) was measured colorimetrically by ferrozine method

As release to groundwater- Batch experiments of IRB

Page 40: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

HFO reducing experiments

0

50

100

150

200

250

0 5 10 15

Time (days)

Fe(

Ⅱ)

(mg/

l)

HFO+IRB+citrateHFO+citrateHFO+IRB+acetateHFO+acetate

As release to groundwater- Batch experiments of IRB

Page 41: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

(a)0

5

10

15

20

25

30

0 5 10 15 20

Time (days)

As

(mg/

l)

As (Ⅲ )

As (Ⅴ )

Total As

(c)0

5

10

15

20

25

30

0 5 10 15 20

Time (days)

As

(mg/

l)

As (Ⅲ )

As (Ⅴ )

Total As

As(V) reducing experiments

(b)0

5

10

15

20

25

30

0 5 10 15 20

Time (days)

As

(mg/

l) As (Ⅲ )

As (Ⅴ )

Total As

(d)0

5

10

15

20

25

30

0 5 10 15 20

Time (days)

As

(mg/

l)As (Ⅲ )

As (Ⅴ )

Total As

As(V) + citrate + IRB

As(V) + citrate + IRB

As(V) + acetate + IRB

As(V) + acetate + IRB

As(V) + citrate As(V) + citrate As(V) + acetate As(V) + acetate

As release to groundwater- Batch experiments of IRB

Page 42: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Results and disscusions

Direct enzymatic microbial reduction of As(V) (arsC)

Detoxification pathway (arsC pathway)

Respiratory pathway (arrA pathway)

As(V)-reducing bacteria are simultaneously cultured of the enrichment experiments

Plausible microbial-mediated processes of As(V) reduction

Page 43: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Results and disscusions

[As(V)-HFO] reducing experiments

(a)0

2

4

6

8

10

12

0 5 10 15 20

Time (days)

As

(mg/

l)

0

50

100

150

200

250

Fe(Ⅱ

) (m

g/l)

As (Ⅲ )As (Ⅴ )Total AsFe (Ⅱ )

(b)

0

2

4

6

8

10

12

0 5 10 15 20

Time (days)

As

(mg/

l)

0

50

100

150

200

250Fe

(Ⅱ) (

mg/

l)

As (Ⅲ )As (Ⅴ )Total AsFe (Ⅱ )

(c)

0

1

2

3

4

5

0 5 10 15 20

Time (days)

As

(mg/

l)

0

20

40

60

80

100

Fe(

Ⅱ)

(mg/

l)

As (Ⅲ )As (Ⅴ )Total AsFe (Ⅱ )

(d)

0

1

2

3

4

5

0 5 10 15 20

Time (days)

As

(mg/

l)

0

20

40

60

80

100

Fe(Ⅱ

) (m

g/l)

As (Ⅲ )As (Ⅴ )Total AsFe (Ⅱ )

[As(V)-HFO] + citrate + IRB

[As(V)-HFO] + citrate + IRB

[As(V)-HFO] + acetate[As(V)-HFO] + acetate[As(V)-HFO] + citrate[As(V)-HFO] + citrate

[As(V)-HFO] + acetate + IRB

[As(V)-HFO] + acetate + IRB

Page 44: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Microbial reduction ofAs(V) by IRB

Reduction of As-rich Feoxy-hydroxides

Biogeochemical processes for As release

As(V) reduction took place after Fe(III) reduction and As(V)desorption, because IRB reduce aqueous As(V) following the

consumption of Fe(III) mineral

Direct enzymatic Indirect processes

Results and disscusions

Page 45: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

This reduction reactions are promoted by IRB Mobilization:

Citrate: desorption of As from the surface of HFO is the

main process of As release Acetate: As release caused by reductive dissolution of HFO

via IRB driven

Transformation: Some IRB have the ability to reduce aqueous As(V) after the

reduction of Fe(III) minerals

As release to groundwater- Batch experiments of IRB

Page 46: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Topic

33

11Where is the As in ground water from ?Where is the As in ground water from ?

Have the As problemsalready been solved ? Have the As problemsalready been solved ?

22How dose the As releaseinto groundwater ?How dose the As releaseinto groundwater ?

Page 47: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Future works

amorphous iron hydroxide (HFO)

Fe(III) Fe(III)

As(V) As(V)

Fe(II) (decrease As(V) sorption sites)

As(V)

As(III)

macromoleculeorganic carbon

degradatedorganic carbon

decrease of sorption sites

e- donor

Mobilization: desorption

aquifer

aquitardanaerobic environmentlow Eh

e- donor

Transport

:competitive desorption :reductive dissolution by IRB

competition of sorption sites

Transformation: reduced by IRB

Conceptual model of As mobilization and transformation in groundwaterConceptual model of As mobilization and transformation in groundwater

Page 48: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

Department of Bioenvironmental Systems Department of Bioenvironmental Systems Engineering NTUEngineering NTU

Page 49: 21 November 2008 Biogeochemical cycling of arsenic in sedimentary basin of southwestern Taiwan Wang, Sheng Wei Department of Bioenvironmental Systems Engineering.

21 November 2008

Thanks for your attention


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