農作物吸收pops研究及其分析 －以多溴二苯醚為例

農作物吸收POP S 研究及其分析 以多溴二苯醚為例

－以多溴二苯醚為例

UPTAKE OF POP S BY CROPS AND ITS ANALYSIS : THE CASE OF

PBDE ^S PBDE ^S

施養信

¹

、楊千瑩

¹

、張美玲

²

、王銘嘉

³

1

台灣大學 農業化學系 台灣大學 農業化學系

2

萬能科技大學 環境工程系

3

中興大學 土壤與環境科學系

I

NTRODUCTION

22

http://www.budgetwater.info/farm-land.jpg http://www.budgetwater.info/farm-land.jpg

I

NTRODUCTION

(http://www.atsdr.cdc.gov/sites/springvalley/newsletter_0202.html)

33

P

ERSISTENT ORGANIC POLLUTANTS

(POP

S

)

44

55

| Although people are mainly exposed to organic

E

XPOSURE PATHWAYS

| Although people are mainly exposed to organic pollutants through inhalation, dermal contact, and ingestion, more than 90% of human exposure

i i ll (POP )

to some persistent organic pollutants (POPs) such as dioxin, polychlorinated biphenyl (PCBs), and organochlorine pesticides (OCPs), and and organochlorine pesticides (OCPs), and polyaromatic hydrocarbons (PAHs) have been through dietary intake (Safe, 1998).

| Uptake of chemicals by vegetation is a major source of food chain bioaccumulation and an source of food chain bioaccumulation and an important route of exposure to humans and animals.

66

A

IR TO

P

LANT

- F

OLIAR

U

PTAKE

(htt // d l /kid / l /4/li ht i ht l)

| Previous studies reported that vegetation probably plays a significant role in contaminants, because

(http://www.eduplace.com/kids/sla/4/lightning.html)

p y g ,

vegetation has much more surface area than the land on which it is growing (Paterson et al., 1990).

| Simonich and Hites (1994) point that plant lipid content and ambient temperatures had a large

ff t th l t' PAH t ti effect on the plant's PAH concentration.

| Most plant surfaces covered with a wax or lipid layer to prevent excessive evapotranspiration so the layer to prevent excessive evapotranspiration, so the pollutant would easily to adsorb to plant from

atmosphere. ₇

atmosphere. ₇

A

IR TO

P

LANT

- F

OLIAR

U

PTAKE

| Therefore, plants even can serve as valuable monitors of atmosphericp concentrations of contaminants.

| Smillie and Waid (1986) has been used Eucalypt foliage for country wide monitoring of PCBs in Australia.

| The atmospheric levels of contaminants could been correlated with vegetation concentrations (Villeneuve et al 1988; Buckley E H 1987;

(Villeneuve et al., 1988; Buckley, E. H., 1987;

Frank and Frank, 1989, Gaggi et al., 1985).

88

99 (Harmenset al., 2013)

(Salam, 2012)

10 10

(Barber et al., 2003)

F

OLIAR AND

R

OOT UPTAKES

| Several reports (Simonic et al., 1995; Waliszewski et al.,

2004 W l 2011 Zh l 2012 ) d

2004; Wang et al., 2011; Zhao et al., 2012;) presented uptake of POPs by crops and its effect on them.

11 11

T

RANSPORT AND

T

RANSFORMATION

MECHANISMS OF ORGANIC

C

ONTAMINANTS MECHANISMS OF ORGANIC

C

ONTAMINANTS

122

Van Aken et al., 2010

P

OLYBROMINATED DIPHENYL ETHER

(PBDE

^S

)

| Polybrominated diphenyl ethers (PBDEs), widely used as flame retardants, raise a serious public concern because they have been found in the concern because they have been found in the environment and also detected in human.

| PBDEs are structurally similar to PCBs and DDT

| PBDEs are structurally similar to PCBs and DDT, therefore, their chemical properties, persistence and distribution in the environment possibly follow the similar patterns.

13 13

M

ASS

T

RANSPORT

B

UDGET OF

PBDE

S

| Dry deposition is an important route to get BDE-209 from the atmosphere to the ground, and soil remains the largest sink.

14 14 Zeng et al., 2010

Fig. . Mass transport budget of BDE-209 within the Pearl River Delta, South China

P

LANTS UPTAKE

O

RGANICS FROM SOILS

| Toxic organic pollutants probably enter the soil and crop

| Toxic organic pollutants probably enter the soil and crop and then they could affect the food safety from these food crops and threat human health.

15

(http://www.uiw.edu/chemistry/chemresearch.html)

15

C

ROPS CONTAMINATED BY ORGANICS THROUGH

C

ROPS CONTAMINATED BY ORGANICS THROUGH

S

OIL AND GROUNDWATER POLLUTIONS

| Agricultural products could be grown in the farms accidentally polluted by organic spills and farms accidentally polluted by organic spills and unaware groundwater contamination.

| Due to the increase of industrial development nowadays, more and more crops could be cultivated in the farms more and more crops could be cultivated in the farms irrigated by incompletely treated wastewaters and unaware emerging organic pollutants.

16 16

C

ROPS

G

ROWN ON OR NEAR CONTAMINATED

S

OILS

http://www.geschichteinchronologie.ch/welt/wasser-u-grundwasser02-d/z002-contamination- groundwater-a-waters-seeping-water-dumping-site-ENGL.jpg

17 17

http://w3.tkgsh.tn.edu.tw/98c426/right%202-2.htm

www.greenpeace.org -

P

ATHWAYS OF POLLUTANT MOVEMENT ACROSS THE ROOT EPIDERMIS AND

CORTEX

.

A: Apoplastic movement

through cell walls and intercellular spaces.

B: Symplastic movement

through cell cytoplasm and plasmodesmata, or transcellularly across cell membranes. y

18 18

(Wild st al., 2005)

19 FIGURE 7. Four xy images showing the degradation of anthracene within the cell walls of the cortex cells of maize: (a) 21 days of grown, with anthracene in blue and anthrone in bright green; (b) 28 days of grown with anthracene in blue/white anthrone in bright green and 19 green; (b) 28 days of grown, with anthracene in blue/white, anthrone in bright green, and anthraquinone in orange; (c) 35 days of growth, with anthracene as blue and anthrquinone as orange; and (d) 49 days of growth, with anthracene in blue, anthrone in green, and

hydroxyanthraquinone in red. (Wild et al., 2005)

20 20 (White, 2002)

SOIL TO

P

LANT

-

ROOT

U

PTAKE

| Root uptake was the main pathway for high molecular weight PAHs taken up from vegetables grown on industrial contaminated soil (Fismeset al., 2002) .

| PBDEs were sorbed into plants from contaminated sewage sludge (Vrkoslavova et al., 2010) .

| Different POPs were found in food items collected in Hong Kong including naphthalene, DDE, beta-, gamma-HCH and PBDE 47 (Qin et al., 2010).

Country Author Year Contaminated conc.

France Joëlle Fismes 2002 Potato and carrot pulp to leaves PAHs : BCF 13.4 ×10⁻⁴to 2 ×10⁻² Czech Republic Jana Vrkoslavova 2010 Nightshade:

BDE 47: 1.6 ng/g dw BDE99: 0 1 ng/g dw

Tobacco：

BDE 47: 5.4 ng/g dw BDE99: 0 1ng/g dw BDE99: 0.1 ng/g dw

BDE100: 0.0 ng/g dw BDE209: n.d

BDE99: 0.1ng/g dw BDE100: 0.1 ng/g dw BDE209: n.d

Hong Kong Yan Yan Qin 2010 Pistachio (開心果): 4.30~10.7 ng/g wet wt

fl d (葵花子) /

21 Sunflower seeds (葵花子): 3.28~8.36 ng/g wet wt

Pumpkin seeds (南瓜子): 2.31~6.49 ng/g wet wt Hawaii nutlet (夏威夷豆): 8.02~15.3 ng/g wet wt Almond (杏仁): 7.35~15.4 ng/g wet wt

C h (腰果) 8 59 14 2 / 21

Cashew (腰果): 8.59~14.2 ng/g wet wt Walnut kernel (核桃): 10.7~19.5 ng/g wet wt Peanut (花生): 5.07~ 10.6 ng/g wet wt

SOIL TO

P

LANT

-

ROOT

U

PTAKE

| PBDEs were found in the plant (Pumpkin, Maize and Ryegrass) which

l i d i l i i i Chi (H l )

cultivated in an electronic waste sites in China (Huanget al., 2011).

22 22 (Huang et al., 2011)

23 23

Huang et al. (2011)

24 (Mueller et al., 2005)

24

(A菜) (白蘿蔔) (紅蘿蔔) (芋頭) (青江菜)

(萵苣)

(碗豆) (茼蒿)

(A菜)

(葱) (芥藍)

(Wang et al 2011) in China

25 (Wang et al., 2011) in China

25

S

ORPTION KINETICS OF FOUR SELECTED ORGANIC COMPOUNDS INTO PLANTS

100 120 140 (a)

100 120 140 (b)

ORGANIC COMPOUNDS INTO PLANTS

0.3 C

60 80 100

Cw(mg/L)

60 80 100

Cw(mg/L) 0.25

k (h-1)

Chinese cabbage Lettuce Scallion Peanut

0 20 40

0 5 10 15 20 25

0 20 40

0 5 10 15 20 25

0.15 0.2

te constant k

Time (hr) Time (hr)

120 140 (c)

120 140 (d)

0.05 0.1

uptake rat

60 80 100

Cw(mg/L)

60 80 100

Cw(mg/L) 0

2 2.5 3 3.5

logK_OW

0 26

20 40

0 5 10 15 20 25

0 20 40

0 5 10 15 20 25

Toluene Xylene 4-Chlorophenol

g _OW

Figure 9. The relationship between the uptake rate constant k and logK_ow.

26

0 5 10 15 20 25

Time (hr)

0 5 10 15 20 25

Time (hr)

Figure 7. Uptake kinetics of xylene (●; ––––), toluene (×; – – –), and 4-chlorophenol (▲; –·–) to (a) Chinese cabbage, (b) lettuce, (c) scallion, and (d) peanut.

I

SOTHERM OF FOUR SELECTED ORGANIC COMPOUNDS INTO PLANTS

1500

2000 (a) 1000

(b)

COMPOUNDS INTO PLANTS

1000 Qplant(mg/kg)

500 Qplant(mg/kg)

0 500

0 50 100 150 200 250

C ( /L)

0

0 50 100 150 200

C ( /L)

Cw(mg/L) Cw(mg/L)

2000 (c)

3000 3500 (d)(c)

1000 1500

Qplant(mg/kg)

1500 2000 2500

plant(mg/kg)

0 27

500

0 50 100 150 200

Q

0 500 1000 Qp

Xylene Toluene 4-Chlorophenol

27

0 50 100 150 200

C_w(mg/L)

0 20 40 60 80 100

Cw(mg/L)

Figure 8. Sorption isotherms of xylene (●; ––––), toluene (×; – – –), and 4-chlorophenol (▲; –·–) to (a) Chinese cabbage, (b) lettuce, (c) scallion, and (d) peanut.

PARTITION MODEL

2

| C_pt/C_w= f_chK_ch+ f_lipK_lip + f_pw

≒ f_chK_ch + f_lipK_ow + f_{pw 1.5} logk_ow＜ 0.2，K_ch＝0

logk_ow＝ 0.1–0.9，K_ch＝0.2 logk ＝ 1 0–1 9，K _h＝0 5

1

Kpl(L/kgplant)

logk_ow 1.0 1.9，K_ch 0.5 logk_ow＝ 2.0–2.9，K_ch＝1 logk ≧ 4.0，K _h＝3

logk_ow＝ 3.0–3.9，K_ch＝2 ^0.5

logK

Chinese cabbage Lettuce Scallion

logk_ow≧ 4.0 K_ch 3

簡化

∵ f_chK_ch＜＜ f_lipK_ow ⁰2 2.5 3 3.5 logK_OW

Scallion Peanut

28

∴

簡化

: C_pt/C_w= f_lipK_{ow Figure 4.} Dependence of log K_plon log K_ow.

28 (Chiouet al., 2001)

90%

100% Lipids Carbohydrates (a)

50%

60%

70%

80% Plant water

% organic compound stored in lipids

= f_lipK_lip/ (f_lipK_lip+ f_chK_ch+ f_pw) ×100

10%

20%

30%

40%

0%

Cabbage Lettuce Scallion Peanut

90%

100% (b)

90%

100% (c)

50%

60%

70%

80%

50%

60%

70%

80%

10%

20%

30%

40%

10%

20%

30%

40%

29

0%

Cabbage Lettuce Scallion Peanut

0%

Cabbage Lettuce Scallion Peanut

Figure 10 Relative contribution of lipids, carbohydrates, and plant water in the sorption of (a) 4- chlorophenol, (b) toluene, and (c) xylene.

29

PARTITION MODEL

7 8

C_eq= C_wK_pl

4 5 6

gKlip

eq w pl

C_eq= C_pw(f_lipK_lip+ f_chK_ch+ f_pw)

2 3 4

log

C_eq= C_wf_lipK_lip,appx

0 1

0 1 2 3 4 5 6 7 8

logK_OW

log K

_lip

= 1.12 log K

_ow

Figure 12. Linear relationship between plant- derived logK_lipand logK_ow. Linear regression yielded log K_lip= 1.12 log K_ow(n=9, R²=0.998).

30 (Chang et al., Ecological Engineering , accepted)

C C (f K +f K ) l K 0 741l K 1 86 ³⁰

C_eq= C_w(f_lip K_ow+f_chK_ch) logK_ch= 0.741 logK_ow－1.86 (Hunget al., 2010)

CULTIVATED BY HYDROPONICS

Fig. 1. Uptake kinetics of 4-BDE into white radish

cultivated by hydroponics. Fig. 2. Sorption capacity of 4-BDE in different parts of white radish cultivated by hydroponics

CULTIVATED BY SILICA SAND

Fi 3 U k ki i f 4 BDE i hi di h Fi 4 S ti it f 4 BDE i diff t t f hit di h Fig. 3. Uptake kinetics of 4-BDE into white radish

cultivated by silica sand.

Fig. 4. Sorption capacity of 4-BDE in different parts of white radish cultivated by silica sand.

CULTIVATED BY SOIL

31 31

Fig. 5. Uptake kinetics of 4-BDE into white radish cultivated by soil.

Fig. 6. Sorption capacity of 4-BDE in different parts of white radish cultivated by soil.

Q_t= αC_w(f_lip K_lip +f_chK_ch)

i ilib i f t ^{(Chiou t l 2001)} Table 2. The calculated quasi-equilibrium factors.

α: quasi-equilibriumfactor ^(Chiouet al., 2001)

Pollutant Kow plant Cultivated

method

quasi- equilibrium factor (αpt)

references factor (αpt)

4-BDE 4.8 White radish hydroponics 0.0015

(施養信等人

4 BDE 4 8 Whi di h ili d 0 0018 (施養信等人,

2012) 4-BDE 4.8 White radish silica sand 0.0018

4-BDE 4.8 White radish soil 0.0001

17ß-E2 3.70 Maize seedling hydroponics 0-0.2

(C d t l α-ZAL 3.88 Maize seedling hydroponics 0-0.6

32 (Cardet al.,

2012)

g y p

E1 3.55 Maize seedling hydroponics 0-0.75 ZAN 4.08 Maize seedling hydroponics 0-0.003 32

C

^ONCLUSIONS

With th i f i d t i l d l t d

| With the increase of industrial development, more and more crops would be under the contamination risk.

| Although the lipid makes up a small fraction of theg p p plant mass, the contribution of lipid on organics sorption in plant is significant.

| The linear correlation between log K the lipid water

| The linear correlation between log K_lip, the lipid-water partition coefficient, and log K_ow, , the octanol-water coefficient, for the aromatic compounds we studied is

d l d t di t th it f t ti f

developed to predict the capacity of vegetation for a chemical.

| Since uptake of organic chemicals by vegetation couldp g y g be a major source of food chain bioaccumulation and an important route of exposure to humans and animals, the trace amount of these POPs in crops needs more 33

the trace amount of these POPs in crops needs more

attention and more studies. ³³

Acknowledgement

• the financial supports from Council of Agriculture in Taiwan .

• all members in my previous department and Organic Chemical Treatment and Fate Lab in NCHU

Treatment and Fate Lab. in NCHU .

• all members in Department of Agricultural Chemistry and Environmental Nanotechnology Lab. in NTU.

T HANK YOU FOR YOUR ATTENTION

T HANK YOU FOR YOUR ATTENTION

Questions and Comments?

Yang hsin Shih

34

Yang-hsin Shih 02-33669442 [email protected]

34