Chlorate Residues in Plant-Based Food: an Update

Ein Bericht aus unserem Laboralltag

Dr. Ingrid Kaufmann-Horlacher

 

Since the publishing of our findings on chlorate residues in plant-based foods at the beginning of March 2014, well over a thousand additional plant-based foods have been examined for the presence of chlorate residues. The most recent analytical data show that, since that publication, the number of samples found with quantities of chlorate residues above the current EU-wide valid MRL of 0.01 mg/kg has decreased. As before, leafy and fruit vegetables are still higher than other foods, and processed/deep frozen vegetables are especially salient in that precisely two-thirds of the analyzed products were detected with chlorate residues over 0.01 mg/kg. The highest amounts in this group were in ready-to-eat carrots, at 0.30 mg/kg, and in deep frozen broccoli, at 0.31 mg/kg. The origin of both products is unknown.

 

Since May 2014 the highest value found has been in basil from Malaysia, at 1.5 mg/kg. Soy beans from China contained 0.56 mg/kg and peeled, cubed mango pieces were detected with 0.65 mg/kg chlorate. There are various possible reasons for the presence of these residues (see Info Box). However, the exact cause for the reduction of samples exceeding the MRL of 0.01 mg/kg seen in our analyses over the last several months is not yet readily clear. Depending on which toxicological reference values and variability factors the evaluation is based on, the possibility of an unwanted, acute health risk cannot be ruled out, at least with the mango cubes.

 

Info Box

Chlorate

Chlorates are the salts of chloric acid; they are strong oxidants and are effective as herbicides and biocides. Since 2008, however, chlorate is no longer authorized for use as a plant protector in the EU. Sodium chlorate may no longer be used in biocide products.

 

The definition for „pesticide residues“ in Regulation (EG) Nr. 396/2005 encompasses residues from plant protector substances in food (including substances no longer authorized), regardless of the source. Chlorate, as a no longer authorized substance, is thereby covered by the EU-wide valid universal standard MRL of 0.01 mg/kg, in accordance with Reg. (EG) Nr. 396/2005.

 

Current Analytical Results

Between May and October 2014 a total of 1,020 plant-based foods were analyzed for chlorate residues within the realm of our routine testing. In 919 of these samples either no chlorate was detected or the quantity of residues was under the MRL of 0.01 mg/kg. The remaining 101 samples (9.9 %) contained chlorate residues above this value. Chlorate residues over 0.1 mg/kg were measured in 16 samples (1.6 %). Our test results, categorized in detail by food type, are depicted in Table 1.

 

 

Chart. 

Illustration 1: Overview of samples tested for chlorate between May and Oct. 2014

 

 

Table 1: Results of analyses from May to October 2014 by food category
Food Category No.
 Analyzed Samples
No. with
Chlorate Residues ≥0.01 mg/kg
% Median mg/kg* Mean mg/kg* Maximum mg/kg Minimum mg/kg

Berries

172

3

1.7

0.016

0.016

0.019

0.012

Leafy Vegetables

161

19

11.8

0.027

0.13

1.5

0.01

Exotic Fruit

61

2

3.3

0.34

0.34

0.65

0.027

Fruit Vegetables

189

27

14.3

0.016

0.037

0.21

0.01

Vegetable Products

44

28

63.6

0.054

0.075

0.31

0.013

Cereals/Cereal Products

25

0

0

       

Legumes

3

1

 

 

0.56

0.56

0.56

Potatoes

17

1

5.9

 

0.019

0.019

0.019

Pome Fruit

69

0

0

 

 

   

Fruit Products

18

1

5.6

 

0.079

0.079

0.079

Mushrooms

24

2

8.3

 

0.077

0.14

0.013

Mushroom
Products

12

6

50.0

0.042

0.084

0.23

0.011

Juices

4

2

 

 

0.011

0.011

0.011

Baby Food

11

3

27.3

0.011

0.017

0.03

0.011

Sprouts

42

1

2.4

 

0.050

0.05

0.05

Stone Fruit

96

4

4.2

0.019

0.038

0.10

0.012

Root Vegetables

30

0

0

 

 

 

 

Citrus Fruit

38

1

2.6

 

0.012

0.012

0.012

Other

4

0

0

 

 

 

 

Total Results

1020

101

9.9

0.025

0.078

1.5

0.01

* Based on samples with quantities ≥0.01 mg/kg.

 

The leafy and fruit vegetable samples, especially the vegetable products, contained higher levels of chlorate residues than the total average. Approximately 12 % of the leafy and 14 % of the fruit vegetables contained residues above 0.01 mg/kg, with a maximum of 1.5 mg/kg in basil from Malaysia. The vegetable product samples were especially notable; a full 63 % of all the samples exceeded the MRL. The highest level measured in this reporting period in this food category was 0.30 mg/kg in ready-to-eat carrots and 0.31 mg/kg in deep frozen broccoli, origin unknown. That a high number of mushroom product samples contained residues can be explained by the fact that, with few exceptions, they were dried mushrooms. However, a sample of preserved mixed mushrooms was striking for its high level of chlorate, at 0.23 mg/kg. All samples analyzed between May and October 2014 that contained chlorate residues above 0.1 mg/kg are summarized in terms of their origin and food category in Table 2.

 

Table 2: Samples (from May-Oct. 2014) with Chlorate ≥ 0.1 mg/kg
Food Category Origin Chlorate in mg/kg

Sweet Cherries

Spain

0.1

Sugar Snaps

Peru

0.11

Basil

Germany

0.12

Broccoli, deep frozen

Germany

0.13

Cultured Mushrooms, fresh

Poland

0.14

Peas, deep frozen

Unknown

0.15

Cultured Mushrooms, Mixed, Dried

Unknown

0.16

Tomatoes

France

0.2

Cultured Mushrooms, Mixed, Preserved

Unknown

0.23

Coriander

Cambodia

0.37

Soy Beans

China

0.56

Mango

Unknown

0.65

Basil

Malaysia

1.5

 

Our test results from the previous months show a reduction in the number of plant-based foods containing chlorate residues. Perhaps manufacturers and marketers have taken positive measures, such as changing the methods of production and processing of food, increasing testing for residues, and rejecting foods with high residues, etc.

 

Table 3: Test results from May to Oct. 2014, based on concentration intervals
  May
2014
June 2014 July 2014 Aug.
2014
Sept. 2014 Oct. 2014

No. Samples Analyzed

196

122

182

167

173

179

No. Samples w/ Chlorate
≤0.01 mg/kg

166

105

167

152

164

164

No. Samples w/ Chlorate
≥ 0.01 mg/kg

30

17

15

15

9

15

≥ 0.01 < 0.02

12

8

7

9

4

4

≥ 0.02 < 0.05

7

4

4

2

1

5

≥ 0.05 < 0.10

6

2

2

3

2

3

≥ 0.10 < 0.5

3

3

2

1

1

3

≥ 0.5  < 1.0

1

0

0

0

1

0

≥ 1.0

1

0

0

0

0

0

 

 

Chart.

Illustration 2: Percentage of samples with chlorate residues based on residue intervals in the months of May to Oct. 2014, compared to data from our March 2014 report on data from 2013.

 

Info Box

How does chlorate end up in plant-based food?
Chlorate residues in plant-based foods can have various causes. These include:

 

Chlorinated irrigation and sprinkling water: treated surface water in addition to well, rain and drinking water can contain chlorate, which can be absorbed by plants. Currently there is no knowledge regarding the possible amount absorbed. Chlorates are toxic to plants (herbicide)

 

Wash/Drinking water: many crops are washed after the harvest, so the water that is used must be suitable. Drinking and well water treated with chlorine-containing biocides contain chlorate in different concentrations. A limit value for chlorate in drinking water has not been determined. It is unlikely that washing products with chlorinated water causes residues much higher than 0.01 mg/kg.


Disinfection measures using chlorine-containing processing water: high concentrations of chlorate can exist in processing water; this procedure can lead to residues in food.


Fertilizer: fertilizers that are contaminated with perchlorate can also contain small amounts of chlorate. However, our analyses of samples containing high amounts of perchlorate residues revealed levels of chlorate no higher than the limit of determination. Samples with chlorate residues very seldom contained perchlorate as well.

 

Use of chlorate as herbicide / Residues from previous applications: there is no current indication that the detected chlorate residues arose from the illegal application of a plant protection product.

 

The analyzed plant-based foods came mostly from EU countries (72 %), and approximately 5 % came from Africa, 7 % from Asia, and 5.2 % from South and Central America. There were 15.5 % more samples with chlorate residues from Asia than from other countries.

 

Table 3: Origin of the analyzed samples (May to October 2014)
Origin No. Samples No. Samples with Chlorate ≥0.01 mg/kg %

Africa

48

3

6.3

Asia

71

11

15.5

EU

737

51

6.9

Europe (non-EU)

8

1

12.5

North America

4

2

50.0

Oceania

6

0

0.0

South and Central America

53

1

1.9

Unknown

93

32

34.4

Total Results

1,020

101

9.9

 

The origin of 93 samples (9.1 %) was unknown. Most of these samples were processed products such as deep frozen or preserved foods, for which there is no obligation to provide the country of origin.

 

Info Box

Labeling the Country of Origin

Most types of fresh fruit and vegetables must be labeled with the country of origin when sold to the consumer. There are some exceptions, however. Table potatoes and new potatoes, fresh bananas, olives, sweetcorn, dates and edible chestnuts without the skin can, but needn’t be, labeled – the trader can give the information voluntarily. For processed foods such as deep frozen fruits and vegetables, preserves, etc., there is no obligation to label the origins of the product.

 

The category „vegetable products“ had the highest percentage of samples containing chlorate residues, at 63 %. This could be an indication that chlorine or substances which produce free chlorine were used during the after-harvest treatment of the crop, e.g., when the food is disinfected in chlorine-containing processing water. This process can lead to the contamination of the products with chlorate, which is a by-product of chlorination (see Info Box).


This situation can be seen especially in carrots. None of the fresh, unprocessed carrots (mostly from EU member states) contained chlorate residues over 0.01 mg/kg, but more than 50 % of the processed carrots showed chlorate residues higher than 0.01 mg/kg. One-third of the ready-to-eat carrots (mostly from the USA), and 100 % of the deep frozen carrots contained chlorate residues above 0.01 mg/kg (see Table 4).

 

Info Box

After-harvest treatment: disinfection procedures with chlorine-containing processing water

One has to distinguish between washing goods with chlorinated drinking water and treating goods with chlorine-containing water as a disinfection procedure. In the latter case the treatment procedure itself is not the most important aspect, but the minimizing of microbial risk via the killing of bacteria. Practically speaking, disinfecting goods with chlorinated drinking water is not possible because, as a result of the washing process, the water becomes organically polluted, which in turn quickly neutralizes the „free chlorine“. Only a continuous supply of chlorine-releasing substances (chloric gas, chlorine dioxide, hypochlorites) ensures a constant concentration of “free chlorine”, which is necessary for the disinfection of food. This procedure produces chlorate as a by-product, which becomes more concentrated in the processing water over time, and can end up in food.

 

Table 4: Test results for carrots, raw and processed (May to October 2014)
 Food Category No.
Samples Analyzed
No. Samples with Chlorate ≥0.01 mg/kg % Mean mg/kg* Maximum mg/kg Minimum mg/kg

Raw Carrots

11

0

0.0

     

Processed
Carrots

9

3

33.3

0.13

0.300

0.043

Deep frozen
Carrots

5

5

100.0

0.085

0.099

0.056

* Based on samples with quantities ≥0.01 mg/kg≥

 

 

Chart.

Illustration 3: Carrots, raw and processed (May to Oct. 2014)

 

Info Box

Legal Assessment

In accordance with Regulation (EG) Nr. 396/2005, the current standard MRL is 0.01 mg/kg.

 

The EU member states are currently assessing the situation regarding contamination of food and drinking water in order to provide data for a toxicological evaluation by the European Food Safety Authority (EFSA). These data will then be the basis for specific MRLs to be determined.

 

The EU Commission suggested temporarily using the following action values for plant-based foods for purposes of enforcement

  • Plant-based foods, excluding vegetables: 0.1 mg/kg
  • Vegetables, excluding carrots: 0.25 mg/kg
  • Carrots: 0.2 mg/kg

 

These values have not yet been officially adopted. Nevertheless, the EU Commission and EU member states have agreed to support control mechanisms regarding the evaluation of toxicological risk.

 

Toxicological Evaluation

Chlorate inhibits, reversibly, the intake of iodine into the thyroid gland and can cause unwanted health effects, especially in sensitive people such as children, pregnant women, or people with thyroid dysfunction. In addition to affecting thyroid function, chlorate can also damage the Erythrocytes (formation of methaemoglobin, haemolysis).

Currently there is no acute reference dose for chlorate available. The Federal Institute for Risk Assessment (BfR) suggested using the value of 0.01 mg/kg bodyweight and day, for chronic as well as acute risk assessment. The risk assessment shall also apply EFSA’s Pesticide Residue Intake Model (PRIMo). Apart from assessments based on the BfR and EFSA’s PRIMo, the EU Commission took no consideration of variability factors in their recommendation of action values for enforcement.

The investigations will continue.

 

For more information, see our Internet articles:

 

Translation

 Catherine Leiblein

 

Artikel erstmals erschienen am 09.04.2015