ARSENIC BIO-ACCESSIBILITY IN RICE BY ON-LINE...

1
ARSENIC BIO-ACCESSIBILITY IN RICE BY ON-LINE LEACHING AND INDUCTIVELY COUPLED PLASMA MASS SPECTROMERY: FOCUS ON THE ARABIC REGION. Beauchemin Diane and Althobiti Randa [email protected] , [email protected] Department of Chemistry, Queen’s University, 90 Bader lane, Kingston, ON K7L 3N6, Canada \ . Irrigation of rice paddies with groundwater rich in arsenic 2 . . Paddy soils contaminated from industrial and mining activity 2 . Figure 1: Sampling sites. A- Results and discussion How does washing affect As level ? for better risk assessment, the rice was evaluated before and after washing step. washing rice has a significant impact on reducing the toxic element content. This chart shows the total concentration of As (n=5) found in rice from different countries. The total concentrations for unwashed and washed rice are in agreement according to a Student`s t-test at 95% confidence level. On-line continuous leaching procedure: 0.2 g of sample is wrapped in quartz wool and placed in a PTFE mini-column. The mini-column is enclosed using plugs of quartz wool. The artificial fluids (saliva, gastric and intestinal) are pumped sequentially through the mini-column while the released arsenic is monitored in real time by ICPMS². Batch procedure: 1 g of sample is placed in a 50-mL falcon tube with saliva, gastric and intestinal fluids added sequentially. Between each addition, the test tube is shaken for 10 min for saliva and 2 hours for other juices at 37 C, followed by centrifugation and collection of supernatants for later analysis². Verification of mass balance: The residue is digested using 2.5 mL HNO 3 , 0.5 mL H 2 O 2 and heated to 50 C for one hour. The final solution is diluted to 25 mL with DDW². B- Results and discussion 0 20 40 60 80 100 120 140 Bio-accessibility % sampling sites of rice Bio-accessibility percentage of As in unwashed samples residue % intestinal % gastric % saliva % 0 20 40 60 80 100 120 140 Bio-accessiblitiy % sampling sites of rice Bio- accessibility percentage of As in washed samples residue % intestinal % gastric % saliva % water % Figure 4: This chart shows the percentage of As leached by each reagent and in the residue for different types of unwashed rice (n=5). The majority of As was leached out by saliva followed by gastric and intestinal juices. Figure 5: The effect of washing is displayed in this chart (n=5). A portion of As is leached out by water prior of cooking. This step can contribute to reduce the toxicity of arsenic in the rice. C- Results and discussion (a) (b) (c) Iraqi rice was found to be the most contaminated with arsenic. Saliva leaches the highest proportion of bio- accessible arsenic. Washing is an essential step prior to rice cooking and consumption. Future work: Develop methods for the speciation analysis of the different leachates by IEC-ICP-MS. Perform the speciation analysis of the bio-accessible fraction from the different rice samples for realistic risk assessment. Conclusion and future work Saudi Arabia for financial support. NSERC for research funding. References : [1] A. Leufroy, L. Noël, D. Beauchemin, T. Guérin, Anal. Bioanal. Chem. 402 (2012) 28492859. [2] N. S. Horner, D. Beauchemin, Anal. Chim. Acta 717 (2012) 16. Acknowledgement and references The goal was to investigate the toxicity of arsenic in Arabic area rice, as well as, to assess the potential risk of environmental arsenic in Arabic area. The effect of washing rice prior to cooking was also assessed to verify if it could make rice safer for human consumption. Arsenic in high concentration can cause a variety of adverse health effects after acute and chronic exposures. Rice analysis is considered essential to ensure the safety for human health, and to produce good quality of food 1 . The concentration of As in rice is often high compared to other crops, with a large fraction present as inorganic arsenic. Yet, rice is a fundamental food in many cultures around the world with average consumption of 100-650 g/person/day. For realistic risk assessment, bio-availability (amount ending up in the blood stream) should ideally be measured. However, as it can only be smaller or equal to bio-accessibility (i.e. the portion dissolved in the gastro-intestinal tract), the latter can be measured instead with an in vitro method, using leaching conditions mimicking those in the human body 2 . Purpose of this study Background A total of 10 rice samples were collected from local markets in Saudi Arabia, such as to represent the Arabic region . They were divided into two groups: Raw rice as purchased from the market . Washed for 5 min and then cooked rice with 30 ml of doubly deionized water (DDW) to 5 g of rice and cooking for 15 min. Varian 820 MS inductively coupled plasma quadruple mass spectrometry. Concentric nebulizer fitted into a Scott double pass spray chamber. Collision-reaction interface to reduce the polyatomic ion interferences. Source of contamination Sample collection Experimental set up Figure 2: Sample introduction of Varian 820 MS. Parameters Optimal setting Ar plasma gas flow rate (L/min) 18 Ar auxiliary gas flow rate (L/min) 1.8 Ar nebulizer gas flow rate ( L/min) 0.99 Ar sheathing gas flow rate (L/min) 0.15 Sample uptake rate (mL/min) 0.8 H 2 CRI gas (mL/min) 80 Table 1: Optimal ICP-MS instrumental parameters for analysis of rice samples Figure 3: Summary of experimental procedure. Methodology Figure 6: Arsenic leaching profile by (a) saliva ; (b) gastric juice; (c) Intestinal juice. the result from the batch method are similar to those obtained using the on-line leaching method (n=5). however, the online leaching method also provide access to real time leaching data. leaching with saliva resulted in the largest peak followed by gastric and intestinal juices. 0 200 400 600 800 1000 1200 As concentration (ng/g) sampling sites of rice the effect of washing process on changing the As concentration in rice samples Wash water Full digestion washed Full digestion unwashed

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ARSENIC BIO-ACCESSIBILITY IN RICE BY ON-LINE LEACHING AND INDUCTIVELY

COUPLED PLASMA MASS SPECTROMERY: FOCUS ON THE ARABIC REGION.

BeaucheminDiane and Althobiti Randa [email protected], [email protected]

Department of Chemistry, Queen’s University, 90 Bader lane, Kingston, ON K7L 3N6, Canada

\

.

Irrigation of

rice paddies

with

groundwater

rich in

arsenic2 ..

Paddy soils

contaminated

from

industrial and

mining

activity2.

Figure 1: Sampling sites.

A- Results and discussion

How does washing affect As level ?

for better risk assessment, the rice was evaluated

before and after washing step.

washing rice has a significant impact on reducing the

toxic element content.

This chart shows the total concentration of As (n=5)

found in rice from different countries. The total

concentrations for unwashed and washed rice are in

agreement according to a Student`s t-test at 95%

confidence level.

On-line continuous leaching procedure:

0.2 g of sample is wrapped in quartz wool and placed

in a PTFE mini-column. The mini-column is

enclosed using plugs of quartz wool. The artificial

fluids (saliva, gastric and intestinal) are pumped

sequentially through the mini-column while the

released arsenic is monitored in real time by ICPMS².

Batch procedure:

1 g of sample is placed in a 50-mL falcon tube with

saliva, gastric and intestinal fluids added sequentially.

Between each addition, the test tube is shaken for 10

min for saliva and 2 hours for other juices at 37 ◦C,

followed by centrifugation and collection of

supernatants for later analysis².

Verification of mass balance:

The residue is digested using 2.5 mL HNO3, 0.5 mL

H2O2 and heated to 50 ◦C for one hour. The final

solution is diluted to 25 mL with DDW².

B- Results and discussion

0

20

40

60

80

100

120

140

B

io-a

cces

sib

ilit

y %

sampling sites of rice

Bio-accessibility percentage of As in

unwashed samples

residue %

intestinal %

gastric %

saliva %

0

20

40

60

80

100

120

140

Bio

-acc

ess

iblit

iy %

sampling sites of rice

Bio- accessibility percentage of As in

washed samples

residue %

intestinal %

gastric %

saliva %

water %

Figure 4: This chart shows

the percentage of As leached

by each reagent and in the

residue for different types of

unwashed rice (n=5).

The majority of As was

leached out by saliva followed

by gastric and intestinal juices.

Figure 5: The effect of

washing is displayed in this

chart (n=5). A portion of As

is leached out by water

prior of cooking. This step

can contribute to reduce the

toxicity of arsenic in the

rice.

C- Results and discussion

(a) (b)

(c)

Iraqi rice was found to be the most contaminated

with arsenic.

Saliva leaches the highest proportion of bio-

accessible arsenic.

Washing is an essential step prior to rice cooking

and consumption.

Future work:

Develop methods for the speciation analysis of the

different leachates by IEC-ICP-MS.

Perform the speciation analysis of the bio-accessible

fraction from the different rice samples for realistic risk

assessment.

Conclusion and future work

Saudi Arabia for financial support.

NSERC for research funding. References :

[1] A. Leufroy, L. Noël, D. Beauchemin, T. Guérin, Anal. Bioanal.

Chem. 402 (2012) 2849–2859.

[2] N. S. Horner, D. Beauchemin, Anal. Chim. Acta 717 (2012) 1–6.

Acknowledgement and references

The goal was to investigate the toxicity of arsenic in Arabic

area rice, as well as, to assess the potential risk of

environmental arsenic in Arabic area. The effect of washing

rice prior to cooking was also assessed to verify if it could

make rice safer for human consumption.

Arsenic in high concentration can cause a variety of adverse

health effects after acute and chronic exposures. Rice analysis

is considered essential to ensure the safety for human health,

and to produce good quality of food1. The concentration of As

in rice is often high compared to other crops, with a large

fraction present as inorganic arsenic. Yet, rice is a

fundamental food in many cultures around the world with

average consumption of 100-650 g/person/day. For realistic

risk assessment, bio-availability (amount ending up in the

blood stream) should ideally be measured. However, as it can

only be smaller or equal to bio-accessibility (i.e. the portion

dissolved in the gastro-intestinal tract), the latter can be

measured instead with an in vitro method, using leaching

conditions mimicking those in the human body2.

Purpose of this study

Background

A total of 10 rice samples were collected from local

markets in Saudi Arabia, such as to represent the

Arabic region . They were divided into two groups:

Raw rice as purchased from the market .

Washed for 5 min and then cooked rice with 30 ml

of doubly deionized water (DDW) to 5 g of rice and

cooking for 15 min.

Varian 820 MS inductively coupled plasma quadruple mass spectrometry.

Concentric nebulizer fitted into a Scott double pass spray chamber.

Collision-reaction interface to reduce the polyatomic ion interferences.

Source of contamination

Sample collection

Experimental set up

Figure 2: Sample introduction of Varian 820 MS.

Parameters Optimal setting

Ar plasma gas flow rate (L/min) 18

Ar auxiliary gas flow rate (L/min) 1.8

Ar nebulizer gas flow rate ( L/min) 0.99

Ar sheathing gas flow rate (L/min) 0.15

Sample uptake rate (mL/min) 0.8

H2 CRI gas (mL/min) 80

Table 1: Optimal ICP-MS instrumental parameters for analysis

of rice samples

Figure 3: Summary of experimental procedure.

Methodology

Figure 6: Arsenic leaching profile by

(a) saliva ;

(b) gastric juice;

(c) Intestinal juice.

the result from the batch method are similar to those

obtained using the on-line leaching method (n=5).

however, the online leaching method also provide access to

real time leaching data.

leaching with saliva resulted in the largest peak followed by

gastric and intestinal juices.

0

200

400

600

800

1000

1200

As

con

cen

trat

ion

(n

g/g

)

sampling sites of rice

the effect of washing process on changing

the As concentration in rice samples

Wash water

Full digestion washed

Full digestion unwashed