INTERFLAME Secondment NIES to AU (3months)related to WP 5 (Knowledge exchange concerning analytical chemistry techniques for measurement on different classes of FRs)

I would like to report regarding results obtained in term of my secondment in prof. Adrian Covaci’s laboratory of Antwerp University (AU) for 3 months during April 1 to June 28, 2013.

Masayuki Someya

So, like this circumstances, in term of my secondment in AU, I learned the GC-ECNI/MS technique which is a useful technique to simultaneously and high sensitively measure the various newly BFRs from prof. Covaci, and I also analyzed the BFRs in soil and sediment samples collected from E-waste recycling site in northern Vietnam which I brought in from NIES.

In NIES, our research group has begun environmental investigations of various contaminants such as BFRs, PFRs, dioxins, heavy metals and other compounds in environmental samples collected in and around E-waste recycling workshops in Asian developing countries to provide useful data for the environmentally sound management of E-waste in the developing countries by identifying critical control process since 2011.

In January 2012, soil and sediment samples were collected from E-waste recycling site in northern Vietnam as part of this research project. Using these samples, we have already got some results for some contaminants such as PBDEs, dioxins and heavy metals in NIES. However, regarding mostly BFRs which were used as replacement of PBDEs, we still could not analyze because analytical methods of mostly BFRs were not established in NIES. However, after phase-out of PBDE usage as BFRs, various newly BFRs were alternatively used in electric devices and therefore it is considered to be a critical issue to assess the contamination status of various BFRs in E-waste recycling site.

Emissions of Newly BFRs from Primitive E-waste Recycling Activities in the Northern Part of Vietnam

INTERFLAME Meeting in Beijing

Masayuki Someya

“E-waste” such as personal computers, TV sets and mobile phones is one of the most increasing rapidly wastes in the world and it was estimated that the rate of E-waste generation globally was approximately 40 million tons per year according to the report by United Nation University (2008).

Background

As everyone knows,

Background

Regarding those E-waste materials, E-waste recyclers and waste brokers are taking advantage of lower recycling costs in developing countries and therefore 80 % of the e-waste in developed countries that is sent for recycling ends up being shipped to developing countries, primarily in Asia and Africa for recycling.

Furthermore, recent study indicated that the developing countries would be disposing of more old computers than developed countries by 2018.

Therefore, huge quantities of E-waste have been widely recycled in not only developed countries but also developing countries.

Moreover, in the developing countries, infrastructure development involved with E-waste recycling activities is not enough and primitive E-waste recycling operations such as manually dismantling of wires and circuit boards, fractionation of metal and plastic, and sorting of electric parts have carried out.

Background

The uncontrolled e-waste recycling activities in developing countries cause serious health and pollution problems, because many of the products contain numerous hazardous chemicals and materials including heavy metals, and POPs such as BFRs, PCBs, dioxins which can pose a threat to the environment and to human health. So, recently, the problem of E-wastes has been of great concern in many developing countries.

However, information on those contaminants in E-waste recycling site are still limited.

Objectives

In present study, our research group attempted to elucidate the contamination status of newly BFRs such as DBDPE, BTBPE, DPs, OBIND and others in soil and sediment samples released from primitive E-waste recycling activities in the northern part of Vietnam.

Regarding obtained newly BFRs concentrations, I would like to discuss compared with PBDEs data.

Sampling Location

E-waste recycling workshop (n=10)

January 2012

Soil (n=32)

Open burning site (n=3)

Paddy field and footpath (n=19)

Sediment (n=8)Upper stream of E-waste workshop(n=1)

In vicinity of E-waste workshop (n=3)

Down stream of E-waste workshop (n=4)

Bui DauHanoi

Bui dau were small rural communes with about 283 households, about 30% of which involved in recycling of metals and plastics from e-waste such as computers, TVs, video players and mobile phones since the early 2000s. In the village, recycling operation such as manually dismantling of wires and circuit boards and fractionation of metal and plastic were family based and conducted in their workplace near their home. Burning of wire and cable for retrieving copper was also performed outside the village as shown in Figure.

1.2km

3.0km

Target compounds

DBDPE BTBPE syn-DP, anti-DP HBBs

TBPH OBIND PBT PBBs α-TBCO, β-TBCO

DPTE PBBA PBEB α-TBECH, β-TBCH TBB

TBCT T23BPIC pTBX HCDBCO BATE

In this study, I analyzed 22 compounds known as newly BFRs which were used instead of PBDEs as shown here.

Analytical Methods

Solvent extraction

Sample

Sieving

Air-Dried

Florisil ENVI cartridge +Copper powder

44% Acid silica

N2 concentration N2 concentration

GC-ECNI-MS GC-ECNI-MS

IS

IS

Average concentrations of newly BFRs and PBDEs in all soil samples collected from E-waste site in northern part of Vietnam

Con

cen

trat

ion

s (p

g/g

dry

wt.

)

BATEpTB

X

HCDBCO

T23BPIC

TBCT

TBB

b-TBEC

H

a-TBCO

a-TBEC

HPBEB

PBBADPTE

b-TBCO

PBBzPBT

OBINDTB

PHHBBz

syn-D

P

anti-D

PBTB

PE

DBDPEPBDEs

0

5000

10000

15000

20000

25000

30000

35000

40000

BATE pTBX

HCDBCO

T23BPIC

TBCT TBB

b-TBECH

a-TBC

O

a-TBECH PBEB

PBBA

DPTE

b-TBC

O PBBz PBTOBIND

TBPH

HBBz

syn-DP

anti-DP

BTBPE

DBDPE

PBDEs

0/32 0/32 0/32 0/32 1/32 1/32 2/32 1/32 3/32 4/32 1/32 3/32 1/32 9/32 5/32 5/32 6/32 10/32 18/32 21/32 11/32 11/32 32/32

These results suggested that E-wastes containing PBDEs were still major E-waste materials to bring into this E-waste recycling site in northern part of Vietnam.

DBDPE, BTBPE, DPs, HBBs, TBPH and OBIND were detected at relatively high concentrations and detection frequency.

PBDEs concentration was the highest, followed by DBDPE, BTBPE, DPs, HBBs, TBPH and OBIND.

These results are indicating that E-wastes materials such as PC, TV set and mobile phones containing the newly BFRs has been brought into this recycling village and the surrounding environment was contaminated by these compounds released with primitive E-waste recycling activities.

610,000180,000

BD-01

BD-02

BD-04

BD-05

BD-06

BD-07

BD-08

BD-09

BD-10

BD-11

BD-12

BD-13

BD-14

BD-15

BD-16

BD-17

BD-18

BD-19

BD-20

BD-21

BD-22

BD-27

BD-23

BD-32

BD-03

BD-24

BD-25

BD-31

BD-26

BD-28

BD-30

BD-29

0

100000

200000

300000

400000

500000

600000

700000

BD-01

BD-02

BD-03

BD-04

BD-05

BD-06

BD-07

BD-08

BD-09

BD-10

BD-11

BD-12

BD-13

BD-14

BD-15

BD-16

BD-17

BD-18

BD-19

BD-20

BD-21

BD-22

BD-23

BD-24

BD-25

BD-27

BD-32

BD-28

BD-30

BD-26

BD-31

BD-29

02000400060008000

1000012000140001600018000

DBDPE

BTBPE

Con

cen

trat

ion

(p

g/g

dry

wt)

Con

cen

trat

ion

(p

g/g

dry

wt)

<LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ

<LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ

footpath in rice paddy open-burning of wires and cables E-waste recycling workshop

For these compounds, the higher concentrations were only detected at samples collected from in vicinity of E-waste recycling workshops.

Spatial distribution of DBDPE and BTBPE concentrations in soil collected from E-waste recycling site in northern part of Vietnam

4,200,000

Con

cen

trat

ion

(p

g/g

dry

wt)

footpath in rice paddy open-burning of wires and cables E-waste recycling workshop

Con

cen

trat

ion

(p

g/g

dry

wt)

BD-01

BD-02

BD-03

BD-04

BD-05

BD-06

BD-07

BD-08

BD-09

BD-10

BD-11

BD-12

BD-13

BD-14

BD-15

BD-16

BD-17

BD-18

BD-19

BD-20

BD-21

BD-22

BD-23

BD-25

BD-27

BD-31

BD-26

BD-24

BD-32

BD-28

BD-30

BD-29

0

2000

4000

6000

8000

10000

12000

14000

16000

<LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ

TBPH

BD-01

BD-02

BD-03

BD-04

BD-05

BD-06

BD-07

BD-08

BD-09

BD-10

BD-11

BD-12

BD-13

BD-14

BD-15

BD-16

BD-17

BD-18

BD-19

BD-20

BD-21

BD-22

BD-23

BD-24

BD-25

BD-27

BD-32

BD-28

BD-30

BD-26

BD-31

BD-29

02000400060008000

1000012000140001600018000 OBIND

<LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ

TBPH and OBIND were also only detected at samples collected from in vicinity of E-waste recycling workshops.

These results suggested that mainly emission source of those compounds in this recycling village were “not-intensive” recycling such as collection, storage and manually dismantling of E-waste.

Spatial distribution of TBPH and OBIND concentrations in soil collected from E-waste recycling site in northern part of Vietnam

Con

cen

trat

ion

(p

g/g

dry

wt)

Con

cen

trat

ion

(p

g/g

dry

wt)

footpath in rice paddy open-burning of wires and cables E-waste recycling workshop

BD-07

BD-09

BD-10

BD-11

BD-12

BD-13

BD-14

BD-16

BD-17

BD-18

BD-19

BD-20

BD-21

BD-22

BD-05

BD-01

BD-15

BD-02

BD-27

BD-04

BD-08

BD-25

BD-32

BD-06

BD-31

BD-23

BD-26

BD-29

BD-24

BD-28

BD-03

BD-30

02000400060008000

1000012000140001600018000 syn-DP

<LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ

BD-01

BD-02

BD-04

BD-05

BD-06

BD-07

BD-08

BD-09

BD-10

BD-11

BD-12

BD-13

BD-14

BD-15

BD-16

BD-17

BD-18

BD-19

BD-20

BD-21

BD-22

BD-27

BD-25

BD-23

BD-31

BD-03

BD-24

BD-28

BD-32

BD-29

BD-26

BD-30

02000400060008000

1000012000140001600018000 HBBs

<LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ

BD-09

BD-10

BD-12

BD-14

BD-16

BD-17

BD-18

BD-19

BD-20

BD-21

BD-22

BD-13

BD-11

BD-05

BD-15

BD-01

BD-07

BD-27

BD-02

BD-25

BD-04

BD-32

BD-08

BD-31

BD-06

BD-23

BD-26

BD-29

BD-24

BD-28

BD-03

BD-30

01000020000300004000050000

anti-DP

Con

cen

trat

ion

(p

g/g

dry

wt)

<LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ

Spatial distribution of DPs and HBBs concentrations in soil collected from E-waste recycling site in northern part of Vietnam

BD-22

BD-20

BD-10

BD-14

BD-16

BD-05

BD-18

BD-09

BD-19

BD-17

BD-21

BD-15

BD-12

BD-02

BD-06

BD-01

BD-07

BD-11

BD-04

BD-13

BD-08

BD-27

BD-23

BD-03

BD-31

BD-26

BD-24

BD-25

BD-32

BD-28

BD-30

BD-29

0

500000

1000000

1500000

2000000

2500000

3000000

deca- nona- octa- hepta- hexa- penta- tetra- tri- di- mono-

Con

cen

trat

ion

(p

g/g

dry

wt)

PBDEs

footpath in rice paddy open-burning of wires and cables E-waste recycling workshop

PBDEs was detected from all soil samples analyzed although soil samples collected from in vicinity of E-waste workshops were higher than other soil samples concentrations.

These results suggested that larger quantity of E-wastes contained not newly BFRs but PBDEs were brought into this E-waste recycling site and/or E-wastes containing PBDEs were recycled for a longer period than E-wastes containing newly BFRs in this village.

If E-wastes containing newly BFRs are continuously brought into this recycling site, contamination of newly BFRs might be also more widely spread to surrounding area of this village like PBDEs in near future. To examine the possibility, further studies are needed for continuous monitoring of newly BFRs contamination in this site.

Spatial distribution of PBDEs concentrations in soil collected from E-waste recycling site in northern part of Vietnam

9,400,000

a-TBEC

H

b-TBEC

H

a-TBCO

b-TBCO

BATEpTB

XPBBz

TBCT

PBTPBEB

DPTEPBBA

TBB

HCDBCO

T23BPIC

HBBzTB

PH

syn-D

POBIND

anti-D

PBTB

PE

DBDPEPBDEs

0

1000

2000

3000

4000

5000

6000

<LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ

0/8 0/8 0/8 0/8 0/8 0/8 0/8 0/8 0/8 0/8 0/8 0/8 0/8 0/8 0/8 4/8 2/8 5/8 1/8 7/8 6/8 5/8 8/8DF

Con

cen

trat

ion

(p

g/g

dry

wt)

Average concentrations of newly BFRs and PBDEs in all sediment samples collected from E-waste site in northern part of Vietnam

For sediment samples, PBDEs concentration was 2-3 order higher than newly BFRs. Detected newly BFRs were only DBDPE, BTBPE, DPs, OBIND, HBBs and TBPH as well as soil samples.

110,000

Spatial distribution of newly BFRs and PBDEs concentrations in sediment collected from E-waste recycling site in northern part of Vietnam

SE-03 SE-01 SE-02 SE-04 SE-05 SE-06 SE-08 SE-070

50000

100000

150000

200000

250000

300000

350000

400000 PBDEs

SE-03 SE-01 SE-02 SE-04 SE-05 SE-06 SE-08 SE-070

5000

10000

15000

20000

25000 DBDPE

SE-03 SE-01 SE-02 SE-04 SE-05 SE-06 SE-08 SE-070

1000

2000

3000

4000

5000

6000

Syn-DPSE-03 SE-01 SE-02 SE-04 SE-05 SE-06 SE-08 SE-07

0

1000

2000

3000

4000

5000

6000 Anti-DP

SE-03 SE-01 SE-02 SE-04 SE-05 SE-06 SE-08 SE-070

200400600800

100012001400160018002000

BTBPE

SE-03 SE-01 SE-02 SE-04 SE-05 SE-06 SE-08 SE-070

50010001500200025003000350040004500 OBIND

Con

cen

trat

ion

(p

g/g

dry

wt)

Upper stream In vicinity of E-waste workshop Down stream Upper stream In vicinity of E-waste workshop Down stream

These results indicated that primitive E-waste recycling activities were point sources for newly BFRs in this site.

Conclusion

For soil samples, although PBDEs concentration was the highest compared with newly BFRs (So, this is a PBDEs contamination story…), DBDPE, BTBPE, DPs, HBBs, TBPH and OBIND were detected at relatively high concentrations.

These results suggested that E-wastes materials containing the newly BFRs has been brought into the recycling village in northern part of Vietnam and the surrounding environment was contaminated by these compounds released with primitive E-waste recycling activities.

These results suggested that mainly emission source of those compounds were different in this recycling site.

Concentrations of DBDPE, BTBPE, TBPH and OBIND were higher in soil samples collected from in vicinity of E-waste recycling workshops. While, concentrations of DPs and HBBs were higher concentrations in soil samples collected from not only in vicinity of E-waste recycling workshops but also near open burning sites of wires and cables.

For sediment samples, the highest newly BFRs concentrations were detected from the site near E-waste recycling workshops and those concentrations demonstrated a tendency to be decreasing with distance from E-waste recycling workshops in the downstream.

These results indicated that primitive E-waste recycling activities were point sources for newly BFRs in this site.

BD-08 BD-06 BD-03 BD-08 BD-06 BD-03DPs (syn+anti) PBDEs

0100002000030000400005000060000700008000090000

100000

open-burning of wires and cables

Con

cen

trat

ion

(p

g/g

dry

wt)