Report on the Organic Monitoring Program of Baden-Württemberg 2020

The Federal State of Baden-Württemberg has been conducting a special monitoring program on organically produced foods since 2002. This monitoring is associated with Baden-Württemberg’s overall concept of promoting organic farming. Organic products are systematically tested for residues and contaminants, as well as other relevant issues. The goal of the organic monitoring program is to prevent fraud by better tracking down cases of improper labeling in this fast expanding market and to strengthen consumers’ confidence in the quality of organically produced foods.

 

Analytical Results from Organic Food Investigations

Detailed information (including results tables) can be found in the German version of the monitoring report.

 

Following is a translation of the topic “Residues from pesticides and specific contaminants in plant-based-foods”.

 

Cover image.

 

Residues from Pesticides and Specific Contaminants in Plant-Based Foods

Introduction

In 2020 a total of 343 samples of plant-based foods from organic cultivation were analyzed for residues of plant-protection substances and particular contaminants. The underlying spectrum of substances routinely analyzed for every sample comprised more than 750 components (active substances and metabolites or degradation products, as well as specific contaminants such as perchlorate, melamine and cyanuric acid).

 

Info Box

Expansion of the Investigative Spectrum and Evaluation of the Data

This year, as in the previous six years, the QuPPe method was routinely used on all samples in order to detect very polar substances that the QuEChERS multi-method cannot capture (see quppe.eu). Representatives of this group include, among others, fosetyl, phosphonic acid, chlorate and perchlorate, but also trimesium (trimethlysulfonium).
To enable the comparison of investigative results for individual years in the future, only specifically chosen, purely chemical/synthetic pesticides, not contaminants, were included in the evaluation.

 

The following substances were listed separately:

  • Substances authorized for use in organic farming: azadirachtin, piperonyl butoxide, pyrethrum, spinosad (see Excursus)
  • Nicotine: different modes of entry possible (see Info Box)
  • Trimethylsulfonium cation: different modes of entry possible or possible formation by processing
  • Fosetyl/phosphonic acid: found in fertilizers and fungicides, long retention time of phosphonic acid in plants/shrubs (see Info Box)
  • Chlorate, perchlorate: different modes of entry possible (see Info Box).
  • Melamine (contaminant): found in fertilizers and as a degradation product of cyromazine
  • Morpholine: additive (used as a carrier substance or emulsifying agent)

 

The following substances will not be considered:

  • Substances occurring naturally in plants: gibberellic acid and other plant hormones (abscisic acid, jasmonic acid, etc.)
  • Bromide: can originate geogenically; amounts < 5 mg/kg assessed as „natural“ amount

 

Fresh Foods

As in previous years, fresh organic fruit and vegetables performed significantly better in 2020 than conventionally produced products. There were no detectable pesticide residues in about 68 % of the organically grown samples (in 2019, 77 %; 2018, approx. 60 %; 2017, 50 %; 2016, 65 %; 2015, approx. 60 %; 2014, 52 %; 2013 and earlier: 60 to 77 %). The findings for this reporting year represent a slight reversal compared to 2019, but correspond to the situation in individual years before 2013.

 

The percentage of samples containing residues of multiple pesticides in 2020 was 11 %, which is higher than in 2019 (6.4 %), but at least similar to the level in 2018 (10.5 %) and significantly lower than that of the years before 2018 (15 % in 2017; 19 % in 2016 and 2015; 21 % in 2014; 12 % in 2013; and 10 % in 2012). After a large spike in 2014, in part contingent on the expansion of the depth of investigations (the analytical spectrum), the numbers over the last five years have dropped significantly, returning to earlier rates.

 

The detected residues were mostly in trace amounts (< 0.01 mg/kg), considerably lower than the concentrations usually found in a harvest where pesticides were used. All in all, the rate of violations in fresh, organically produced foods has stabilized at a low level over the last few years, and has dropped significantly since the beginning of the organic monitoring program more than 19 years ago.

 

In 2020 two organic fruit samples (bananas from Ecuador and the Dominican Republic) and three organic vegetable samples (garlic from Spain and parsley and coriander from Germany) were judged to have been falsely labeled organic, due to the detection of increased levels of pesticide residues.

 

The rate of violations in this reporting year for organic fruit was 3.0 % (2.4 % in 2019) and for organic vegetables 2.2 % (1.0 % in 2019). The rate of violations for all organic fresh foods in the years from 2011 to 2019 was always well under 5 %, while the rates before 2010 were significantly higher, with numbers as high as 8.5 %. In this reporting year (overall rate of 2.4 %), there were neither any accumulation of violations for organic fruits, nor any other irregularities in single cultures detected, as in past years. In the years before 2009 there were intermittent anomalies found: herbicides in broccoli and carrots from Italy, the fungicidal substance fosetyl in cucumbers from different countries, surface treatment substances and acaricides in citrus fruits, and sprout inhibitors in potatoes.

 

Average Pesticide Amounts in Fresh Foods

Average pesticide amounts found in the samples can be an indication of the presence of plant protection substances, as the following tables show.

 

Average pesticide residues per sample (in mg/kg)

Fruit
2013
2014
2015
2016
2017
2018
2019
2020
Organically produced samples
0.008
0.005
0.002
0.001
0.002
0.004
0.003
0.004
Conventionally produced samples (excluding surface treatment substances or preservatives, phosphonic acid and bromide)
0.32
0.42
0.35
0.43
0.45
0.40
0.45
0.44

 

Vegetables
2013
2014
2015
2016
2017
2018
2019
2020
Organically produced samples
0.004
0.001
0.002
0.003
0.003
0.008
0.002
0.004
Conventionally produced samples (excluding phosphonic acid and bromide)
0.38
0.32
0.49
0.46
0.36
0.46
0.41
0.29

 

The average amount of pesticide residues detected in all analyzed organic fruit and vegetable samples this reporting year was 0.004 mg/kg each, when all organically labeled samples (including those with false labeling) are included in the calculation. Exclusion of the samples that were in violation, suspected of being conventionally produced or cross-bred with conventional products, yielded averages of 0.002 and 0.003 mg/kg respectively. These average sum amounts have remained low over the last years (see table).

 

The averages for conventionally produced fruit lay at 0.44 mg/kg (excluding surface treatment substances, phosphonic acid and bromide) and for vegetables at 0.29 mg/kg (excluding phosphonic acid and bromide). The reason for the higher amount of pesticide is due to the application of chemical plant protection substances that are authorized for conventional cultivation, the residues of which are often unavoidable in the treated plant cultures. A detailed body of regulations provides consumers with a measure of safety, however, as long as the maximum residue levels are not exceeded.

 

Since the use of chemical synthetic pesticides is not permitted in organic cultivation, very few samples, if any, tend to have residues over 0.01 mg/kg. The organic products differ significantly from conventional goods in terms of contamination from pesticide residues, which the organic monitoring program has clearly demonstrated over the past 19 years.

 

Processed Foods

The rate of violations (due to false organic labeling) among processed foods in this reporting year was 2.4 %, the same as for fresh fruit and vegetables (2.4 %), so low as has been seldom achieved in previous years, and almost the same level as last year (2.6 % in 2019). The rate has remained at a range of 2.2 % to 7.0 % over the past several years; before 2011 it was generally > 8 %.

 

It must be considered, however, that the focus on particular processed organic products changes from year to year and that short-term projects carried out on this product group have only recently come into sharper focus. The comparability of violation rates from year to year and over the entire course of the organic monitoring program is therefore limited.

 

Individual anomalies (in single food groups) among the processed foods analyzed in 2020 were only found in frozen herbs and dried cereal grasses. These involved one sample each of frozen dill and frozen parsley, due to an elevated quantity of chloridazon (herbicide) and/or its degradation product chloridazon-desphenyl, as well as one sample of barley grass (dried powder) containing residues of the growth regulator dikegulac. In this reporting year, as in 2019, there was no accumulation of violations (from false organic labeling) in a particular food category. Last year (2019) there had been 4 violations: 2 samples of deep frozen herbs, also due to chloridazon/chloridazon-desphenyl and 2 of dried herbs (bay leaves due to acetamiprid and oregano due to tebuconanzole).

 

One can also refer to the chapter on “Special Findings”, where results and data for special substances or projects and food groups that are excluded from these explanations are given separate attention. These require a separate observation, either due to their particularities in occurrence, application, possible modes of entry and analytics, or because they present new or separate problems.

 

When making a judgment regarding the amounts of residues in processed foods, valid drying and processing factors for the specific substances must be considered because the processing of the original product can lead to an increase or decrease of residues (see Info Box regarding processing factors).

 

Info Box

Consideration of Processing Factors

As a rule, Regulation (EC) No. 396/2005 stipulates the maximum level of residues from plant protection substances to be permitted for unprocessed foods. However, the amount of pesticide residues in and on unprocessed foods can change as a result of certain processing factors. This regulation mandates, therefore, that legal judgments regarding the determined quantities of pesticide residues in processed food take into account such processing factors (e. g. the production of dried fruit and herbs, canned products, wine, flour or bread). In a few cases it is impossible to make a final judgment because processing factors for certain substances or matrices are not always known. When there are low levels of substances in the product, there is also a greater degree of computational uncertainty. These drying and processing factors are not legally binding, however, because no pertinent conclusive legal ordinance exists, nor is there any chart in which they are listed.

 

Regulation (EC) No. 396/2005 actually foresees the establishment of a separate annex for such legally binding factors, but so far no such annex exists. Also included in this regulation, but with, as of yet, no entries of maximum residue limits, is a main category of “processed foods”.

 

Overview of Violations

The following table gives an overview of all organic samples analyzed in 2020 for residues of pesticides and their rate of violations, itemized by food group.

 

Overview of organic samples analyzed in 2020
Type of Sample
No. of Samples
Samples with residues > 0.01 mg/kg(2)
Average amount per sample, in mg/kg(2)
No. samples falsely labeled as „organic“
Samples > MRL(3)
Vegetables (incl. potatoes and starch-rich plant parts)
139
4 (2.9 %)
0.004
3 (2.2 %)
Parsley leaves from Germany (orthophenylphenol) , Coriander from Germany (metamitron), Garlic from Spain (prochloraz, sum; tebuconazol)
2 (1.4 %)
Parsley leaves from Germany (orthophenylphenol), Artichokes from France (biphenyl)
Vegetable Products
13
3 (23 %)
(fresh product)
0.012

0.012
(fresh product)
2 (15 %)
Frozen Dill unknown origin and frozen parsley from Germany (both chloridazon, sum or degradation product chloridazon-desphenyl)
-
-
Fruit
66
3 (4.5 %)
0.004
2 (2.4 %)
Bananas from Ecuador (orthophenylphenol); Bananas from the Dom. Republic (epoxiconazole)
3 (4.5 %)
2x Bananas from Ecuador (both orthophenylphenol), Bananas from the Dom. Republic (fipronil, sum)
Fruit products
3 (1)
-
(fresh product)
0.006

0.001
(fresh product)
-
-
-
-
Fresh mushrooms and their products
4 (1)
-
(fresh product)
0.032

0.004
(fresh product)
-
-
-
-
Legumes (dried), oil seeds, nuts,soy products
37
4 (11 %)
0.005
-
-
2 (5.4 %)
Hazelnuts (ground) unknown origin (pirimiphos-methyl), Red Lentils (dried) unknown origin (chlorpyrifos)
Cereals
25
-
0.001
-
-
-
-
Cereal products
13
-
0.001
-
-
-
-
Wine, wine products: wine grapes
10
1 (10 %)
0.007
1 (10 %)
Wine grapes „Souvignier Gris“ from Germany (folpet)
-
-
Spices
6
-
(fresh product)
0.027

0.007
(fresh product)
-
-
-
-
Tea (black and green tea)
2 (1)
-
(fresh product)
0.003
 

0.001
(fresh product)

-
-
-
-
Plant powder (red beet, broccoli, barley- and wheat grass, moringa, spirulina- and chlorella-algae)
22
2 (9.1%)
(fresh product)
0.026
 

0.004
(fresh product)

1 (4.5 %)
Barley grass powder from Germany (dikegulac)
2 (9.1 %)
2x Barley grass powder from Germany (both dikegulac)
Other (olive oil, apple juice)
3 (1)
-
0.008
-
-
-
-
TOTAL
343
17 (5.0 %)
-
9 (2.6 %)
-
9 (2.6 %)
-

1) No calculated percentages for sample sizes < 5
2) With consideration of processing factors for the respective processed products and without consideration of the separately listed substances found in the section „Special Findings“, or the substances authorized for use in organic farming
3) MRL = Maximum residue level established by Regulation (EC) No. 396/2005; formal objections due to substances in the chapter “Special Findings” are not included.

 

Excursus

Detected Substances Authorized for Organic Farming in 2020

Among the substances that are authorized for organic farming under European Organic Regulations (EC) No. 834/2007 and No. 889/2007 (see positive list in Annex II) and that are tested and detected regularly are the insecticides azadirachtin A, pyrethrum (pyrethrins), spinosad and the synergist piperonyl butoxide. Piperonyl butoxide strengthens the insecticide effect of, e. g. pyrethrins, but has no insecticidal effect itself.

 

The following table shows the substances authorized for organic farming that were found in the samples analyzed in 2020:

 

Substance
Frequency
Product
Amount [mg/kg]
Azadirachtin A
5
Basil
Bell pepper
Chili pepper
Sweet cherry (2 samples)
0.007
0.015
0.010
0.007 / 0.013
Pyrethrum
0
-
-
Piperonyl butoxide
2
Rose hip powder
Hazelnut, ground
0.011
0.032
Spinosad
17
Banana (2 samples)
Pear
Clementine
Lambs lettuce
Cucumber (2 samples)
Blueberry
Wine grape
Spinach (3 samples)
Table grape (3 samples)
Tomato (2 samples)
0.001 / 0.002
0.001
0.001
0.018
0.004 / 0.010
0.009
0.020
0.002 / 2.2 / 3.4
0.005 / 0.017 / 0.020
0.014 / 0.020

 

The rate of detection for these substances among the total of 343 analyzed samples was 7.0 % (6.4 % in 2019; 4.8 % in 2018; 4.2 % in 2017; 9.9 % in 2016; 8.6 % in 2015; and 10.4 % in 2014). Other substances authorized for use in organic farming such as natural oils, sulphur, copper or ferrous salts were not analyzed as part of these investigations.

 

Special Findings

In the following section residue data and results for special substances or projects/food groups are presented that were excluded from the observations made thus far. They require individual consideration, either due to unique characteristics regarding their existence, applications, possible modes of entry and analysis, or because they present new or special problems.

 

Nicotine

Info Box

Nicotine

Nicotine is a neurotoxin that is harmful to humans and, in higher amounts, to insects (insecticide). It can occur naturally in plants of, e. g. the nightshade family (solanaceae); however, except for tobacco plants, the amount is low. This substance is among the most poisonous pesticides ever authorized for use in Europe. Although nicotine is still used to some extent in third countries (as an active ingredient in pesticides or for the preparation of tobacco), its use in pesticides has been banned in Europe since 2010 as a result of its high toxicity (acute reference dose: 0.0008 mg/kg bodyweight). Exposure to nicotine can still come from contact with smokers, however. Regardless of its path of entry, nicotine falls under the area of applications in Regulation (EC) No. 396/2005.

 

In 2017 CVUA Stuttgart published the report “Nicotine from tobacco – a ‚natural‘ substance against plant pests?“ on the topic of tobacco brew. At the beginning of 2019 CVUA Stuttgart published another report on this topic, entitled “Nicotine in Food: What Does Smoking Have To Do With It?“. This report documented our analytical results and provided information on our model trials, to show to what extent relevant levels of nicotine can end up on food when a person smokes and then comes in direct contact with food.

 

The Chemical and Veterinary Investigations Office (CVUA) Stuttgart established a refined method several years ago with preliminary screening for analyzing the parameters of nicotine in plant-based matrices. In this reporting year a total of 343 samples from organic cultivation were analyzed for nicotine. Of these, 6 samples (1.8 %) contained nicotine > 0.01 mg/kg, compared to 13 of 358 (3.6 %) in 2019; 9 of 355 (2.5 %) samples in 2018; and 19 of 324 (5.7 %) samples in 2017.

 

This rate is half that of 2019, with almost the same number of samples analyzed. One of the samples (0.3 %), dried white beans from China, was in violation due to a verified exceedance of the maximum residue level of 0.01 mg/kg. There were no violations in 2019, but one sample (0.3 %) in 2018 and four samples (1.2 %) in 2017 exceeded the limit.

 

One sample (0.3 %) exceeded the limit, albeit without verification within the measurement uncertainty (kale from Germany). These cases were highlighted in a report drawing attention to the increased residue levels. In 2018 and 2019 there were also two samples each (0.6 %) that were reported for violation.

 

It is important to note here that nicotine residues can have various paths of entry (see Info Box) that are to be considered and discussed. An overview of the analyzed samples containing detectable amounts of nicotine, itemized by matrix, is presented in the following table.

 

Residues of Nicotine in Samples from Organic Cultivation (2020)
Matrix / Type of Sample
Amount of Nicotine [mg/kg]
Maximum Residue Level [mg/kg]
Kale
0.014
0.01
Moringa oleifera powder (2x)
0.17 / 0.24
0.5
White beans, dried
0.036
0.01
Porcini mushrooms, dried
0.22
2,3
Black tea (Ceylon tea)
0.087
0.6

 

In 2017, due to conspicuous, low-level findings (< 0.01 mg/kg) of nicotine in plant-based foods, we carried out model trials to determine to what extent the consumption of tobacco could lead to the transfer of nicotine from a smoker’s hands to food (see the 2017 organic monitoring report). The experiments showed that, shortly after having smoked a cigarette, measurable amounts of nicotine could be transferred from the smoker’s hands onto fruits and vegetables. The transfer of nicotine to moist foods was even higher, reaching the low-set legal maximum residue levels in some cases.

 

CVUA Stuttgart reports on possible contaminants and sources of contamination; however, since the mode of entry and/or the cause of detected nicotine residues is usually not known, the „organic“ labeling of such foods is not judged to be fraudulent. Nevertheless, an indication is made in the report that a documented, intentional application of nicotine containing plant protection substances would constitute such an offence.

 

Regardless of its mode of entry, however, nicotine is subject to the MRL established by Regulation (EC) No. 396/2005. Analyses of nicotine residues will continue in 2021.

 

Trimethylsulfonium cation (Trimesium)

In 2020 all 343 samples of organic produce were analyzed for residues of the substance trimethlysulfonium cation (trimesium).

 

Trimethlysulfonium cation is listed in Regulation (EC) No. 396/2005 as a substance that forms as a result of the use of glyphosate. Trimesium is not formed as a result of the usage, however, but rather exists in plant-protection substances as a counterion to glyphosate; it is already in the completed formulation. Such types of pesticides are still authorized for use in non-EU states, but no longer within the EU. Due to its particular properties, this substance cannot be integrated into the investigative spectrum of the QuEChERS multi-method; it requires its own processing and analytical method.

 

Residues of trimethlysulfonium cation were detected in 16 (4.7 %) samples (compared to 11 of 358 (3.1 %) in 2019: 6 of 355 (1.7 %) in 2018; 28 of 324 (8.6 %) in 2017): Six (1.7 %) of these were verified to be over the maximum residue level (with consideration of drying factors). These included two samples of red beet powder and one each of rose hip powder, moringa leaf powder, black tea, and green tea. Four (1.2 %) further samples, including two of red beet powder and one each of broccoli and rose hip powder, were nominally, but unverified, above the maximum level. The legal maximum level for all of the listed samples and matrices lies at 0.05 mg/kg. There were no anomalies for this substance in the previous two years, while in 2017 there were still 10 of 324 analyzed samples (3.1 %) in violation.

 

The following table shows an overview of the analyzed samples with determinable residue amounts, itemized by matrix.

 

Residues of Trimethlysulfonium Cation in Samples from Organic Cultivation (2020)
Matrix / Type of Sample
Amount of
Trimethlysulfonium Cation [mg/kg]
Plant powder, dried:
Moringa oleifera
Barley grass (3x)
Red Beet (4x)
Broccoli
Rose hip (3x)

0.13
0.028 / 0.033 / 0.059
0.59 / 0.68 / 0.81 / 1.5
0.66
0.084 / 0.38 / 1.1
Black tea (Ceylon tea)
Green tea (Matcha)
0.13
0.13
Red beet, fresh (2x)
0.006 / 0.008

 

There are indications, however, that the contaminant trimethlysulfonium (trimesium) found in tea and other dried foods occurs as a result of processing, during the drying procedure. The analytical results show that higher amounts appear mainly in dried samples. Further investigations and process controls are necessary, in order to determine whether the formation of trimesium via drying can be reduced through an appropriate method. Any enforcement actions in Baden-Württemberg will be curtailed until a final clarification can be made on this issue.

 

Reports on such findings indicate possible paths of entry and formation in the particular matrices. Regardless of its paths of entry into the specific food, however, trimethlysulfonium cation, as well as the aforementioned nicotine, falls under the applications area in Regulation (EC) No. 396/2005 and is subject to the maximum residue limits provided therein. Trimesium will be further analyzed in 2021.

 

Phosphonic Acid / Phosphonates / Fosetyl

In this reporting year all of the 343 samples from organic culture were also analyzed for the fungicidal substances fosetyl and phosphonic acid. In regulation (EC) No. 396/2005 these substances are registered as sum parameters of fosetyl (sum of fosetyl and phosphonic acid and their salts, expressed as fosetyl).

 

It is important to note that residues from phosphonic acid can have various causes and therewith various (possible) paths of entry (see Info Box on phosphonic acid and fosetyl). Residues can thus stem from applications that don’t serve as plant protection.

 

Neither of these substances is integrated into the investigative spectrum of the QuEChERS multi-method due to their particular properties; they require their own processing and analytical methods.

 

Info Box

Phosphonic Acid and Fosetyl

Both fosetyl and phosphonic acid are fungicides that are permitted for use in the EU and fall under the applications area of Reg. (EC) No. 396/2005, regardless of their path of entry. Neither of these substances is authorized for use in organic farming, but there are current discussions regarding the future inclusion of phosphonic acid in the positive list of substances authorized for use in organic farming in Annex II of the EU Organic Ordinance.

 

Detected quantities of phosphonic acid can result from the use of a fungicide that contains potassium phosphonate or fosetyl aluminum. An application of a phosphonate-containing fertilizer, a so-called leaf fertilizer, is also conceivable. Such an application is no longer possible, however, because phosphonate was classified as a fungicide (pesticide substance) in the harvest year of 2014. High levels of phosphonic acid could also stem from an earlier application, because plants tend to retain this substance for a long time, possibly even years. There is evidence that plants store phosphonic acid and only gradually release it over a period of time.

 

The following table shows an overview of the samples with detectable residues, itemized by individual product groups or matrices.

 

Residues from phosphonic acid and/or fosetyl in samples from organic production (2020)
Matrix / Type of Sample
Amount of
Phosphonic Acid [mg/kg]
Sum Fosetyl [mg/kg]
(Sum of Fosetyl and Phosphonic Acid, expressed as Fosetyl)
Avocado (2x)
Ginger, fresh (2x)
Onion, red
0.22 / 0.44
0.13 / 1.6
0.32
0.30 / 0.59
0.17 / 2.1
0.43
Millet (2x)
Corn kernels / -meal
Buckwheat kernels/ -meal
0.58 / 0.59
0.52 / 0.45
0.30 / 0.27
0.78 / 0.79
0.70 / 0.60
0.40 / 0.36
Lentils, dried (3x)
Kidney beans, dried
0.40 / 0.57 / 0.95
0.43
0.54 / 0.77 / 1.3
0.58
Sesame, unhulled
Chia seeds
0.48
0.46
0.64
0.62
Ginger powder
0.87
1.2
Maracuja nectar
0.21
0.28
Wine grapes, white
Wine grapes, red (3x)
0.12
0.24 / 0.24 / 2.7
0.16
0.32 / 0.32 / 3.6

 

In 2020 a total of 23 of the 343 samples (6.7 %) contained residues, whereby a significant decrease can be seen over the past few years and the value from this reporting year is in the realm of that from the previous year ((21 of 358 samples (5.9 %) in 2019; 8.7 % in 2018; 8.3 % in 2017; 14 % in 2016; 15 % in 2015; 19 % in 2014; and 24 % in 2013)). A certain plateau could have been reached here.

 

These residues occurred in a variety of different matrices, from diverse countries of origin, and thus cannot be limited to single types of food or individual countries. There was a very wide range of detectable levels of phosphonic acid, from trace amounts of just over 0.1 mg/kg (0.12 mg/kg) to a peak value of 1.6 mg/kg in a fresh ginger sample and 2.7 mg/kg in a sample of red wine grapes. Residue amounts > 5 or even > 10 mg/kg, as were found intermittently in previous years, were not recorded in this reporting year.

 

Also of interest is the fact that only residues from phosphonic acid were found in all of the analyzed samples, whereas no residues of fosetyl per se were detectable. This points to the likelihood of a fertilizer application, as was also the case in previous years.

 

Because the source of the phosphonic acid residues can‘t be determined in the laboratory (see Info Box on phosphonic acid and fosetyl), 22 samples with residue amounts > 0.1 mg/kg, taking processing factors into consideration (compared with 22 cases in 2018, 21 in 2017 and 43 in 2016), were highlighted in a report with the goal of raising awareness among the producers, so that they would attempt to identify the possible paths of entry. One sample of avocado had residue amounts, with consideration of the pit, of just under 0.1 mg/kg, so no commentary was submitted.

 

One of the 343 analyzed samples (0.3 %, compared to 0.6 % or 2 of 358 samples in 2019) exceeded the valid maximum sum levels for fosetyl (sum of fosetyl and phosphonic acid and their salts, expressed as fosetyl) stipulated by Regulation (EC) No. 396/2005, albeit unverified. This was a sample of fresh ginger, with a sum residue amount of 2.1 mg/kg, just above the legal maximum level of 2 mg/kg. It was also observed that the range of maximum levels for the sum of fosetyl is very wide, ranging from values of 2 mg/kg for many matrices, up to values as high as 2,000 mg/kg (!) in hops.

 

Chlorate and Perchlorate

In 2020 all 343 samples from organic cultivation were analyzed for chlorate and for the environmental contaminant perchlorate (see Info Boxes).

 

The following table presents an overview of the analyzed samples with detectable amounts, itemized by matrix. For reasons of clarity, only samples containing chlorate in amounts > 0.01 mg/kg (formal MRL) and perchlorate > 0.05 mg/kg (lowest EU reference value until end of June, 2020) are included in the chart. New, higher legal maximum levels for chlorate have been valid since July 1, 2020, between 0.05 and 0.7 mg/kg (excluding baby food, at 0.01 mg/kg); for perchlorate the new legally binding levels are set between 0.05 and 0.75 mg/kg for matrices other than baby food (0.01 or 0.02 mg/kg). The results of our analyses will be explained following the table.

 

Quantities of Chlorate and Perchlorate in Organic Samples (2020)
Matrix / Type of Sample Quantity of
Chlorate [mg/kg]
Quantity of
Perchlorate [mg/kg]
Parsley leaves, fresh
Basil, fresh
Chard
Chives, fresh
Kale
Spinach
Zucchini
Tomato
Ginger, fresh
Cucumber
Arugula/Roman Rocket
Head lettuce
Red beet, fresh
Celery (stalk)
Banana
Table grapes, red
Lime
Oats grains
Millet grains
Lentils, red, dried
Parsley (frozen)
Dill (frozen)
Broccoli (frozen)
Sesame
Chia seeds
Barley grass powder
Red beet powder
Moringa oleifera powder
Apple juice

0.041
0.012
0.011

0.017
0.011/ 0.014
0.036
0.045
0.020
0.060
0.020
0.018
0.024
0.023/ 0.036
0.027
0.012
0.011
0.011
0.038

0.016
0.070
0.036
0.26

0.034

0.013
0.059

0.051

0.055 / 0.075
0.058 / 0.082




















0.14
0.070 / 0.30
0.41 / 1.6 / 1.8

 

Residues of perchlorate were detected in 67 of the 343 (20 %) analyzed organic samples (compared to 17 % in 2019; 22 % in 2018; 23 % in 2017; 17 % in 2016; 20 % in 2015; 31 % in 2014; and 19 % in 2013). Residues of chlorate were detected in 49 (14 %) samples (compared to 13 % in 2019; 11 % in 2018; 16 % in 2017; 12 % in 2016; 16 % in 2015; 20 % in 2014, and 26 % in 2013).

 

As was the case with phosphonic acid, these findings were also dispersed over a wide variety of matrices and countries of origin, and could not, therefore, be reduced to individual types of food or countries. Similar to fosetyl and phosphonic acid, the properties of these two substances prevent them from being integrated into the investigative spectrum of the QuEChERS multi-method; they require their own processing and analytical method.

 

Chlorate and perchlorate have been routinely analyzed within the scope of the organic monitoring program since 2013. These substances will also play an important role in investigations in 2021.

 

Perchlorate

In line with the European Contamination Regulation (EEC) No. 315/93, reports on organic samples with elevated levels of perchlorate (> 0.1 mg/kg, based on the fresh product) were submitted, in order to promote investigations into their causation and to encourage measures to minimize the amounts. In 2020 there were only three (0.9 %) such cases from organic cultivation (3.1 % in 2019; 1.0 % in 2018; 2.5 % in 2017; 2.4 % in 2016; 2.0 % in 2015; and 2.2 % in 2014). All three of these samples were moringa oleifera leaf powder, two of which (0.6 %) exceeded with verification the reference value for perchlorate of 0.75 mg/kg; the third one lied under this value.

 

These two samples would have also exceeded with verification the new legal maximum levels for perchlorate established in the EU maximum level for contaminants ordinance (Regulation (EC) No. 1881/2006) that have been valid since July 2020. These samples were collected and analyzed well before the date of validity, however, so they were assessed as having exceeded the then valid EU reference value. These reference values were not legally binding, but should have ensured the marketability of the products. Considering all 343 analyzed samples in view of the new, legal maximum levels, aside from the two above-mentioned samples, no further sample exceeded these levels.

 

CVUA Stuttgart addressed the issue of perchlorate eight years ago. With the reduction of fertilizer use, the amounts found in plant-based foods have sunk in the meantime. Nevertheless, the Federal Institute for Risk Assessment (BfR) has recommended a further reduction due to toxicological concerns. These newly established EU-wide MRLs are an important step and represent a major success for consumer and health protection, for which CVUA Stuttgart has played a meaningful role.

 

Info Box

Perchlorate

Perchlorates are the salts of perchloric acid. They are generally soluble in water, and exist permanently in the environment. The industrial use of perchlorates is extensive and diverse: they are used in the metal processing industry, in paper finishing, as a diuretic and oxidant, and as explosive and incendiary devices. According to a report by the Federal Environment Agency, this widespread industrial use of perchlorate could be a cause of food contamination. Perchlorate finds its way into the food chain via, e. g. contaminated sludge that is used in agriculture (not, however, in organic agriculture) or by other components from such processes. It can also be assumed that these substances are found ubiquitously in small concentrations in rain water and contaminated environmental compartments such as in the water cycle and soil. It is also known that perchlorates occur from fertilizers and artificial irrigation. Analyses conducted on fertilizer based on chile saltpeter revealed high levels of perchlorate. Particular fertilizers used especially in greenhouse cultivation cause the enrichment of perchlorate in soil.

 

Chlorate

A total of 26 of the 343 (7.6 %) analyzed samples contained chlorate residues > 0.01 mg/kg (7.0 % in 2019; 3.9 % in 2018; 6.8 % in 2017; 6.2 % in 2016; 11 % in 2015; 16 % in 2014). Although there are known possible paths of entry, it cannot be said with absolute certainty where the residues in a particular sample came from (see Info Box on chlorate). Until the end of the previous year (2019), samples with verified MRL exceedances (chlorate values > 0.02 mg/kg with consideration of processing and drying factors) were officially reported to be in violation. In this reporting year there were 12 (3.5 %) such cases (3.6 % in 2019; 1.7 % in 2018; 3.1 % in 2017; 1.9 % in 2016; 3.3 % in 2015; 7.3 % in 2014).

 

Assessments for the year 2020 took into account the anticipated new maximum levels to be valid from July 2020, however. These are set between 0.05 and 0.7 mg/kg, with the exception of baby food (0.01 mg/kg). Only 3 of the 343 analyzed samples (0.9 %) contained any residue levels above the lowest maximum quantity of 0.05 mg/kg (arugula/Roman rocket, frozen broccoli and chia seeds). Only the sample of chia seeds was reported for violation of the new, valid maximum level of 0.05 mg/kg, with verification, while the arugula/Roman rocket and broccoli samples lay under the new values of 0.7 mg/kg and 0.4 mg/kg, respectively.

 

In 2015 the European Food Safety Authority (EFSA) published new toxicological assessments regarding chlorate residues in food (acute reference dose of 0.036 mg/kg bodyweight and day). Based on these assessments, none of the samples analyzed in 2020 exceeded these health-based reference values. That means none exhausted the values by more than 100 %, and posed thereby no chronic or acute health problems.

 

Info Box

Chlorate

Chlorates are effective as both herbicides and biocides. Since 2008, however, chlorate is no longer authorized for use as a pesticide* in the EU. Sodium chlorate may also no longer be used in biocide products.

 

The definition for „pesticide residues“ in Regulation (EC) No. 396/2005 also encompasses residues from pesticide substances in food (including substances no longer authorized) that have pathways other than from the use of plant protectant products (so-called dual-use substances), such as the case of chlorate in food. Until the inception of the changed maximum levels from July 2020, chlorate was thereby covered by the EU-wide valid default MRL of 0.01 mg/kg, in accordance with Reg. (EC) No. 396/2005. In 2017 in Germany maximums of 70 µg/l chlorate for long-term use and 200 µg/l chlorate for short-term dosages were established for drinking water when the disinfection could not be otherwise guaranteed**.

 

The presence of chlorate in food can result not only from its use as a pesticide, but also due to environmental pollution (contaminated sprinkling- or irrigation water and soil), or as a residual of food production techniques, including methods used in farming, manufacturing, processing, preparation, or treatment. The application of biocides, from which chlorate can result, poses another possible source of contamination. In general, chlorate can be formed as a by-product of the disinfection of drinking/ non-potable water with chloric gas, hypochlorite, or chlorine dioxide.

 

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)***. The application of chlorate in the food chain should therefore be further reduced.

 

The EU member states carried out a several years long monitoring program to determine the degree of contamination in food and drinking water, in order to provide data for a toxicological evaluation by the European Food Safety Authority (EFSA). Specific MRLs as already mentioned were then established based on this information.

 

Sources: Federal Institute for Risk Assessment (BfR), European Commission

* Commission Decision of 10 November 2008 concerning the non-inclusion of chlorate in Annex I to Council Directive 91/414/ECC and the withdrawal of authorizations for plant protection products containing that substance (OJ of the EU L307/7 of 18 November 2008)

** Chlorate in drinking water

*** Federal Institute for Risk Assessment (BfR), recommendations for the health assessment of chlorate residues in foods, from 12 May 2014 (accessed on 8 March 2019)  

 

Hydrogen Phosphide (Phosphine)

These days food is imported to Germany from all over the world. In some cases the goods will have traveled a very long way in ships or other transporters before they arrive. The fumigant hydrogen phosphide is often used in the form of its phosphide salts in sea containers in order to protect the goods from storage pests during transport. The salts applied as solids in dispensers react with moisture in the air, creating hydrogen phosphide which, when released, kills the pests. Phosphine is also used in storage rooms, where dry or dried goods are stored.

 

Phosphine or hydrogen phosphide is not authorized for use in organic cultivation, so residues are not to be expected. Natural occurring contamination from phosphine is to date not known or proven. There are discussions, however, regarding the possibility of (cross) contamination from residual dust of previously stored treated or gassed goods that clings to the inner walls of containers or storage halls and which, when not properly cleaned, can be transferred to untreated goods.

 

In this reporting year CVUA Stuttgart analyzed 28 organic samples especially for residues of the fumigant hydrogen phosphide (phosphine). In the years 2017 to 2019 phosphine residues were found mainly in dried legumes (lentils), so this food group was again made a focus of this year’s analyses (13 samples were analyzed; see tables below). There was also special attention made to cereal kernels, such as rice, maize, rye, and millet (11 samples; see tables).

 

Phosphine residues were detected in nine of the 28 (32 %) analyzed samples (33 % in 2019; 14 % in 2018; 12 % in 2017), which involved lentils (5x), beans (1x), rice (2x), and spelt flour (1x). Eight of these samples (29 %; 22 % in 2019) contained only trace amounts of < 3 µg/kg (0.003 mg/kg), whereas one sample of basmati rice from Pakistan contained levels of 5.8 µg/kg (0.0058 mg/kg). This sample was referenced in an assessment report, due to its slightly higher residues. This fell, however, significantly short of the maximum level established by regulation (EC) No. 396/2005 of 50 µg/kg (0.05 mg/kg).

 

In this year, then, no organically grown samples were found to be in violation, either due to an exceedance of the maximum residue level or to the fraudulent labeling of a conventionally grown product as organic. In the previous year (2019), however, a sample of lentils from Turkey was indeed registered as violatory.

 

As a comparison:

In 2020 analyses for phosphine residues were conducted on 34 samples from conventional cultivation (see table below). Nineteen samples (56 %; 73 % in 2019) contained residues in detectable amounts, most under 10 µg/kg (0.01 mg/kg). Four samples, however, were above this level ((between 11.3 and 197 µg/kg (0.011–0.197 mg/kg)). One sample of dried lentils from Turkey exceeded the legally established MRL of 10 µg/kg (0.010 mg/kg) with verification, and was reported for violation. The MRL exceedance of another sample of lentils from Turkey was unverified in consideration of the measurement uncertainty of 50 %; likewise with a sample of brown rice from India (MRL of 50 µg/kg or 0.05 mg/kg).

 

In 2019 four samples of dried lentils (2x Turkey, 1x Russia, 1x unknown origin) with an exceedance of the maximum level were reported for violations. Three of these cases were verified, and the fourth was unverified.

In 2019 and 2020 there were significantly more residues detected in conventional food than in previous years. It is important to note, however, that the analytical limit of detection of the applied measurement methods was lowered in 2019, so much lower levels were and are able to be determined.

 

CVUA Stuttgart published a report (in German) on its internet website with background information on the subject of residues from the fumigant hydrogen phosphide in arid, plant-based foods as early as 2012.

 

Residues of Hydrogen Phosphide in Samples from Organic Cultivation (2020)
Matrix / Type of Sample
No. of Samples
No. Samples > Maximum Level
No. Samples with Residues
Legumes, dried (lentils, beans)
13
0
6 (46 %)
Cereals (kernels)
11
0
2* (18 %)
Cereal products
3 (1)
0
1
Nuts
1 (1)
0
0
TOTAL
28
0
9 (32 %)

* One sample of basmati rice with residue level of 5.8 µg/kg (MRL: 50 µg/kg): report was submitted with regard to organic, as residues > 5 µg/kg; all other samples had residues < 3 µg/kg
1) No average calculated for sample sizes < 5

 

Residues of Hydrogen Phosphide in Samples from Conventional Cultivation (2020)
Matrix / Type of Sample
No. of Samples
No. Samples > Maximum Level
No. Samples with Residues
Legumes, dried (lentils, beans)
17
2* (12 %)
9 (53 %)
Cereals (kernels)
9
1* (11 %)
7 (78 %)
Cereal products
4 (1)
0
1
Nuts
4 (1)
0
2
TOTAL
34
3 (8,8 %)
19 (56 %)

* Two samples of lentils with residue levels of 12.9 µg/kg and 197 µg/kg (MRL: 10 µg/kg) and a sample of brown rice with residue levels of 63.0 µg/kg (MRL: 50 µg/kg)
1) No average calculated for sample sizes < 5

 

Remarkable and interesting individual samples and findings from reporting year 2020

Dikegulac in Organic Barley Grass Powder

Three samples of organic barley grass powder contained residues of dikegulac in amounts of 0.054 mg/kg, 0.17 mg/kg and 0.18 mg/kg. One of these samples exceeded, verified, the valid amount of 0.01 mg/kg with consideration of drying factors; a second sample was nominally, but unverified, above the limit, and a third sample lay just under the maximum level.

 

The substance dikegulac is a growth regulator that minimizes, e. g. the length of grasses. It has not been authorized for use in the EU since the early 2000s, however. Between the years of 1960 and 1999 dikegulac ended up in the environment in the region “Hessisches Ried” via sewage water resulting from the industrial production of Vitamin C there. Dikegulac was detected in organic spinach grown in the area as recently as the end of 2018/beginning of 2019, according to local media reports (Wiesbadener Kurier on 07/12/2018): “Contaminated Water, Contaminated Vegetables: High Concentrations of Plant Protector Dikegulac Found in Groundwater of Hessisch Organic Farmer’s Field.”

 

Three of the organic barley samples analyzed by CVUA in 2019 (see also 2019 report) were also detected with dikegulac in amounts of between 0.008 and 0.018 mg/kg. These samples were traceable to the above-mentioned area in Hessen. Whether the three samples of barley grass powder from 2020 also came from this area is not known, unfortunately, and must still be investigated.

 

Melamine in Organic Foods

Melamine is not a substance occurring in pesticides, but is rather a contaminant, for which a general maximum level of 2.5 mg/kg in food has been established, in accordance with EU Contaminant Ordinance No. 1881/2006. Melamine is included in CVUA Stuttgart‘s analytical spectrum, so every sample is routinely examined for it. Melamine was detected in 20 of the 343 (5.8 %; 9.5 % in 2019) organic samples analyzed in 2020, at levels above 0.01 mg/kg. The amounts found in four of these samples (1.2 %; 3.9 % in 2019) were above 0.1 mg/kg. These included two samples of moringa oleifera leaf powder with 0.24 and 0.26 mg/kg, one sample of garlic with 0.17 mg/kg and one sample of arugula/Roman rocket with 0.20 mg/kg. Although one sample of organic potatoes had been detected with residue levels of 6.3 mg/kg in 2019, which exceeded the above mentioned maximum levels, verified, and was thus reported for a violation, there was not one sample from this year.

 

Melamine can end up in food via fertilizers that release calcium cyanimide or which themselves contain melamine. It can also conceivably come from an application of the insecticide cyromazine, which forms melamine as a byproduct. Such fertilizers as well as cyromazine are not authorized for use in organic cultivation, however.

 

Chloridazon-Desphenyl in Frozen Herbs and Vegetables from Organic Cultivation

The by-product of the herbicide chloridazon was detected in two samples of organically grown frozen herbs (parsley and dill), two samples of frozen spinach and one sample of frozen green beans. The MRL set by regulation (EC) No. 396/2005 was not exceeded. The residues detected in the two parsley and dill samples were significantly and verifiably higher than the orientation value for organic goods of 0.01 mg/kg, however. The application of chemical synthetic plant protectors such as chloridazon is not permitted in organic farming in general. These two samples were therefore judged to be fraudulent due to their organic labeling. The other three samples (spinach and green beans) were all slightly under 0.01 mg/kg.

 

There were also detectable amounts of chloridazon-desphenyl found in three samples of organic frozen herbs (dill and chives) last year (2019). Two of these were reported as fraudulent in terms of the organic labeling; the third sample was referenced as containing slightly raised amounts.

 

Chloridazon is no longer permitted for use in the EU, but since the country of origin is (usually) not indicated on frozen goods it is possible that the herbs come from third countries.

 

Morpholine in Organic Products

In 2019 two samples of organic smoothies were found to contain the additive morpholine, a substance unauthorized for use in the EU. In the past morpholine was used as a stabilizer and emulsifier in wax for the surface treatment of exotic, citrus and stone fruits from South America, South Africa and Southeast Asia. In that case, follow-up research revealed that the morpholine ended up in the drink via the chlorella algae that was also used in the drink. Further direct investigations into chlorella algae from organic aquaculture by CVUA Stuttgart in this reporting year have now shown that these products can exhibit very high levels of morpholine (around 20 mg/kg).

 

Whether chlorella algae naturally contains morpholine, whether it was treated with morpholine as part of its farming production, or whether it resulted from contamination must be further investigated.

 

In the course of tracing the origins of a violatory sample of chlorella algae containing residues of morpholine in the amount of 18.7 mg/kg, in 2020, the following facts were determined:

The chlorella algae came from China and the morpholine resulted from contamination of the algae due to contact with a lubricant that had been used in conditioning the tank that held the algae. The source of the contamination was herewith declared, and the organic status of the affected parties was removed. The manufacturers/producers in China were instructed to take measures that would hinder such contamination in the future. Any export by chlorella algae producers will only be permitted in the future if the results from a morpholine analysis are presented without any detectable residues.

 

Inorganic Bromide in Organic Products

Higher levels of bromide (degradation product of the fumigant methyl bromide) are sometimes detected in our analyzed samples, both organic and conventional. Bromide can also occur naturally in soil, however, and there is indication that in areas near the sea or in former marine areas the naturally occurring amounts of bromide can be higher. Italy and other countries often refer to this as a possible source of bromide residues. Taking this fact into account, residue amounts of up to 5 mg/kg (orientation or threshold value) in fresh organic products will be accepted as having come from natural sources. In this reporting year 15 of the 343 (4.4 %) analyzed samples showed amounts of > 5 mg/kg.

 

In its assessment reports CVUA Stuttgart highlights cases where higher amounts of bromide residues in organic samples of > 10 mg/kg were detected (verified exceedance of the orientation value, under consideration of possible processing or drying factors). There were four (1.2 %) such cases in 2020: 2 samples of hulled sesame seeds from India, basmati rice from India, and green lentils from an unknown origin. Moreover, the two sesame seed samples exceeded the legal maximum level of 20 mg/kg for sesame, in accordance with regulation (EC) No. 396/2005, although this was not verified with regard to analytical measurement uncertainty.

 

A fast and effective fumigant, methyl bromide has been long and widely used; however, it is very damaging to the ozone layer. Therefore, 175 countries made an international contract in 1987 (the Montreal Protocol) in which they pledged to significantly limit the use of methyl bromide as a fumigant and to apply alternative methods until 2015. Since 2015 the application of methyl bromide has been strictly limited worldwide. A reductionary trend in bromide residue amounts is therewith to be expected in the coming years.

 

Authors

Marc Wieland, Kathi Hacker and Ellen Scherbaum, CVUA Stuttgart

 

Translated by: Catherine Leiblein

 

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Report published on 23.11.2021 09:19:48