Report on the Organic Monitoring Program of Baden-Württemberg 2022
Report from a day in the lab
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
Following is a translation of the topic “Residues from pesticides and specific contaminants in plant-based-foods”.
Residues from Pesticides and Specific Contaminants in Plant-Based Foods
Introduction
In 2022 a total of 423 samples of plant-based foods from organic cultivation were analyzed for residues of plant-protection substances and specific contaminants. The underlying spectrum of substances for which every sample is routinely analyzed comprises more than 700 components (active substances and metabolites or degradation products as well as particular contaminants such as perchlorate, melamine and cyanuric acid). Including screening methods, this spectrum exceeds 1,000 substances.
Info Box
Expansion of the Investigative Spectrum and Evaluation of the Data
This year, as in the previous eight 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, as well as also trimesium (trimethlysulfonium cation).
To enable future comparison of investigative results for individual years, 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 possible modes of entry (see Info Box)
- Trimethylsulfonium cation: different possible modes of entry or formation during processing
- Fosetyl/phosphonic acid: contained in fertilizers and fungicides; long retention time of phosphonic acid in plants/shrubs (see Info Box)
- Chlorate, perchlorate: different possible modes of entry (see Info Box).
- Melamine (contaminant): contained in fertilizers or as a degradation product of cyromazine
- Morpholine: additive (used as a carrier substance or emulsifying agent)
- Ethylene oxide, phosphine (fumigants): used mainly for protection during transport and storage and for the disinfecting and sterilizing of food
The following substances were not 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 2022 than conventionally produced fresh products. There were no detectable pesticide residues in 75 % of the organically grown samples (76 % in 2021; 68 % in 2020; 77 % in 2019; just under 60 % in 2018; 50 % in 2017; 65 % in 2016; just under 60 % in 2015; 52 % in 2014; and 60 to 77 % in 2013 and earlier). The rate for this reporting year is almost identical to the years of 2021 and 2019 and somewhat higher than the value in 2020, but it continues to achieve a high level.
The percentage of samples containing residues of multiple pesticides in 2022 was 7.0 % which, although slightly higher than in 2019 (6.4 %), was lower than in the years 2021 (8.7 %), 2020 (11 %), and 2018 (10.5 %) and significantly lower than in the years before 2018 (15 % in 2017; 19 % in 2016 and 2015; 21 % in 2014; and 12 % in 2013). After a large spike in 2014, in part contingent on the expansion of the depth of investigations (the analytical spectrum), the averages over the last five years have dropped significantly.
Only trace amounts (< 0.01 mg/kg) of residues were detected, which are considerably lower than the concentrations usually found in harvested crops where pesticides had been 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 organic monitoring program began 21 years ago. In 2022 in the category of organically labelled fresh fruit and vegetables, two samples of oranges and one of kiwi, both from Italy, as well as one sample of bell peppers from Spain were judged to be fraudulent due to the presence of high levels of pesticide residues. However, it must be noted that, although the two samples of organic oranges came from the same distributer, they were taken from different points of sale. In the previous year (2021) not a single sample was deemed fraudulent, whereas in 2020 two organic fruit samples (bananas from Ecuador and the Dominican Republic) and three organic vegetable samples (garlic from Spain, parsley and coriander from Germany) were so.
In 2021 there were no cases of fresh organic food samples containing pesticide residue levels exceeding the legally valid maximum levels as stipulated in regulation (EC) No. 396/2005. However, in 2022 there was one organic sample (tomatoes from Spain). In this case the substance tetramethrin was detected in amounts just above the maximum level; however, the exceedance was not analytically verified, given the measurement uncertainty of 50 %. This active substance is not authorized for use in the EU as a plant protector, but is widely used as a biocide in household pesticide products.
The rate of violations in this reporting year for organic fruit was 3.4 % (0 % in 2021; 3.0 % in 2020; and 2.4 % in2019) and for organic vegetables 0.8 % (0 % in 2021; 2.2 % in 2020; and 1.0 % in 2019). The rate of violations for all organic fresh foods in the years from 2011 to 2020 stayed well under 5 %, while the rates before 2010 were significantly higher, with averages as high as 8.5 %. In this reporting year (overall rate of 1.8 % compared to 0 % in 2021 and 2.4 % in 2020), 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
The mere presence of plant protection substances can be seen by the average amounts of pesticide found in the samples, as the following tables show.
Average pesticide residues per sample (in mg/kg)
Fruit |
2015
|
2016
|
2017
|
2018
|
2019
|
2020
|
2020 |
2022
|
---|---|---|---|---|---|---|---|---|
Organically produced samples |
0.002
|
0.001
|
0.002
|
0.004
|
0.003
|
0.004
|
0.002
|
0.005
|
Conventionally produced samples (excluding surface treatment substances or preservatives, phosphonic acid and bromide) |
0.35
|
0.43
|
0.45
|
0.40
|
0.45
|
0.44
|
0.48
|
0.38
|
Vegetables |
2015
|
2016
|
2017
|
2018
|
2019
|
2020
|
2021
|
2022
|
---|---|---|---|---|---|---|---|---|
Organically produced samples |
0.002
|
0.003
|
0.003
|
0.008
|
0.002
|
0.004
|
0.002
|
0.003
|
Conventionally produced samples (excluding phosphonic acid and bromide) |
0.49
|
0.46
|
0.36
|
0.46
|
0.41
|
0.29
|
0.40
|
0.46
|
The average amount of pesticide residues detected in all analyzed organic fruit samples this reporting year was 0.005 mg/kg, and for all analyzed organic vegetable samples, 0.003 mg/kg, when all organically labelled samples, also those with fraudulent organic labeling, were included in the calculation. The averages dropped to 0.003 and 0.002 mg/kg, respectively, when suspect samples were excluded. Such samples involved those that had been conventionally produced, those mixed with conventional products, and those that were not in conformity with organic farming regulations as evidenced by the pesticide residue situation. The average amounts have remained low over the last years, with very little variation (see table).
Conventionally produced fruit contained an average of 0.38 mg/kg plant protector residues (excluding surface treatment substances, phosphonic acid and bromide) and vegetables 0.46 mg/kg (excluding phosphonic acid and bromide). The reason for the higher amount in vegetables is due to the application of chemical plant protection substances that are authorized for conventional cultivation; residues are often unavoidable in the treated plant cultures. An extensive 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 21 years.
Processed Plant-based Foods
The rate of violations (due to false organic labeling) among processed foods in this reporting year was 2.2 %, only slightly higher than the rate of 1.8 % for fresh organic ware, but still at the constant lows of previous years (3.1 % in 2021; 2.4 % in 2020; and 2.6 % in 2019). The rate for processed foods has remained between 2.2 % and 7.0 % since 2011, whereas before 2011 it was generally > 8 %.
It must be considered, however, that, due to the ever increasing availability of new products, short-term projects are carried out from year to year on specific processed organic product groups that have 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 2022 were found in dried fruits and various oilseeds. These involved one sample of dried pineapple (origin: Ghana) with residues of haloxyfop (herbicide); one sample of flaxseed (origin: Kazakhstan) with residues of diquat (herbicide); two samples of chia seeds (one from Paraguay, with residues of paraquat (herbicide) and one from an unknown origin, with residues of pirimiphos-methyl (after harvest/storage insecticide)). The two substances diquat and paraquat have only been integrated into the spectrum of routinely analyzed substances since 2022, when methods for their analysis became available.
In this reporting year, as in the past few years, there was no accumulation of violations (from false organic labeling) in a particular food category. In the previous year (2021) there were five samples of note: frozen chives (unknown origin), due to elevated quantities of chloridazone (herbicide) or its degradation product chloridazone desphenyl; almonds (origin: U.S.A.) with residues of glufosinate (herbicide); dried goji berries (origin: China) with residues of flonicamid (insecticide); dried figs (origin: Turkey) with chlorpyrifos-methyl (insecticide/acaricide); and dried pineapple (origin: Ghana) with haloxyfop (herbicide). In 2020 there were three such samples: frozen dill and frozen parsley due to elevated quantities of chloridazone/chloridazon-desphenyl and barley grass (dried powder) with residues of dikegulac (growth regulator). In 2019 there were 4 samples in violation: 2x frozen herbs with chloridazone/chloridazone/-desphenyl and 2x dried herbs (bay leaves with the insecticide acetamiprid; and oregano with the fungicide tebuconazole).
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, 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).
In this reporting year, two of the analyzed samples (1.0 %) exceeded the valid maximum residue levels, analytically verified, taking processing factors into consideration. These included dried pineapple (origin: Ghana; haloxyfop) and chia seeds (origin: Paraguay; paraquat). Another sample of chia seeds (origin: Bolivia) exceeded the legal limit for haloxyfop, but this was not analytically verified.
In the previous year (2021), three samples (1.9 %) were found to have exceeded valid maximum levels, analytically verified: dried figs (chlorpyrifos-methyl), dried pineapple (haloxyfop), and dried moringa leaf powder (chlorantraniliprole and lambda-cyhalothrin).
Info Box
Consideration of Processing Factors
As a rule, Regulation (EC) No. 396/2005 stipulates the maximum levels of plant protection substance residues allowed for unprocessed foods. The amount of pesticide residues that are present in and on unprocessed foods can change during the processing procedures, however. 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. changes resulting from the production of dried fruit and herbs, preserves, 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 would actually necessitate a separate appendix for such legally binding factors, but this has not yet been established. Also covered by this regulation, but not yet provided with maximum residue levels, is the general category “Processed Foods”.
Overview of Violations
The following table gives an overview of violations for organic samples analyzed over the last several years. Fortunately, this rate has decreased in general, and has been consistently < 5 % over the last five years (2018 to 2022).
Year |
2017
|
2018
|
2019
|
2020
|
2020
|
2022
|
---|---|---|---|---|---|---|
Rate of violations |
7.9 %
|
3.9 %
|
3.1 %
|
3.7 %
|
1.6 %
|
1.9 %
|
The following table gives an overview of all organic samples analyzed in 2022 for residues of pesticides and their rate of violations, itemized by food group (matrix).
Type of sample |
Total no. samples
|
Samples with residues > 0.01 mg/kg
|
Samples with violations:“organic“ is misleading 1)
|
Samples with amounts > maximum residue level 2)
|
Average amount per sample, in mg/kg 3)
|
||
---|---|---|---|---|---|---|---|
Vegetables (incl. potatoes and starch rich plant parts) |
136
|
2 (1.5 %)
|
1 (0.7 %)
|
Bell pepper from Spain (cypermethrin, total)
|
1 (0.7 %)
|
Tomatoes from Spain (tetramethrin)
|
0.003
|
Vegetable products |
18
|
0
(fresh product) |
0
|
-
|
0
|
-
|
0.009
0.005 (fresh product) |
Fresh fruit |
89
|
5 (5.6 %)
|
3 (3.4 %)
|
2x Oranges from Italy(2x acetamiprid); Kiwis from Italy (fludiocxonil)
|
0
|
-
|
0.005
|
Fruit products |
21
|
1 (4.8 %)
(fresh product) |
1 (4.8 %)
|
Dried pineapple from Ghana (haloxyfop, sum)
|
1 (4.8 %)
|
Dried pineapple from Ghana (haloxyfop, sum)
|
0.056
0.011 (fresh product) |
Fresh mushrooms |
3
|
0
|
0
|
-
|
0
|
-
|
0.005
|
Legumes (dried), Oilseeds, Nuts, Soy products |
48
|
5 (10 %)
|
3 (6.3 %)
|
Flaxseed from Kazakhstan (diquat); Chia seeds from Paraguay (paraquat); Chia seeds Unknown origin (pirimiphos-methyl)
|
2 (4.2 %)
|
Chia seeds from Paraguay (paraquat); Chia seeds from Bolivia (haloxyfop, sum)
|
0.006
|
Cereals |
44
|
0
|
0
|
-
|
0
|
-
|
0.004
|
Cereal products (flour, flakes, spelt crumbs) |
15
|
1 (6.7 %)
|
0
|
-
|
0
|
-
|
0.005
|
Vegetarian and vegan substitute products (drinks, „quark“, „joghurt“) |
16
|
0
|
0
|
-
|
0
|
-
|
0.002
|
Baby food |
16
|
0
|
0
|
-
|
0
|
-
|
0.002
|
Spices |
9
|
0
(fresh product) |
0
|
-
|
0
|
-
|
0.019
0.005 (fresh product) |
Wine, wine grapes |
3
|
0
|
0
|
-
|
0
|
-
|
0.007
0.002 (fresh product) |
Other (plant-based oil, juice, tea) |
5
|
0
|
0
|
-
|
0
|
-
|
0.003
|
TOTAL |
423
|
14 (3.3 %)
|
8 (1.9 %)
|
-
|
4 (0.9 %)
|
-
|
-
|
Excursus
Authorized and substances detected in organic farming in 2022
New regulations for organic farming ((Regulation (EC) No’s. 2018/848 and 2021/1165)) came into effect in 2022. These regulations specify which substances are authorized for use in organic farming (see positive list in Annex I of Regulation (EC) 2021/1165). These include 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. These authorized substances are also investigated and regularly detected in organic foods, as the following table shows.
Substance |
Frequency
|
Product
|
Amount [mg/kg]
|
---|---|---|---|
Azadirachtin A |
2
|
Arugula / rocket (2 samples)
|
0.055 / 0.43
|
Pyrethrum |
1
|
Bell pepper
|
0.046
|
Piperonyl butoxide |
1
|
Tomato
|
0.038
|
Spinosad |
12
|
Broccoli
Arugula / rocket Pear (2 samples) Blueberry (2 samples) Mandarine Orange Lemon Table grapes Wine, red Fruit preparation for babies and young children |
0.004
1.0 0.040 0.001 / 0.025 0.001 0.001 0.002 0.055 0.004 0.001 |
The rate of detection for these substances among the total of 423 analyzed samples was 3.8 % (4.0 % in 2021; 7.0 % in 2020; 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
Residue data and results from special substances and food groups or projects that have been thus far excluded from the observations are presented in the following section. 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
In 2022 all 423 samples from organic production were analyzed for residues of nicotine.
The Chemical and Veterinary Analysis Agency (CVUA) Stuttgart already established a refined method several years ago with preliminary screening for analyzing the parameters of nicotine in plant-based matrices. Due to findings of low levels (under 0.01 mg/kg) of nicotine in plant-based foods, a model trial was carried out in 2017 to determine to what extent the consumption of tobacco products would cause nicotine to transfer from hands onto food (see here the Organic Monitoring report from 2017, pg. 17; CVUA Stuttgart | Report on the Organic Monitoring Program of Baden-Württemberg 2017). These investigations showed that nicotine could indeed be transferred to fruit and vegetables in measurable amounts when a smoker touched these foods shortly after having smoked a cigarette. The transfer of nicotine was even higher for wet foods, such that the detected amounts reached the low-set legal maximum levels in some cases.
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 of 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.
CVUA Stuttgart has already published 2 reports; firstly, in order to report on the investigative results and secondly, to inform the public about our model trial in which we showed the extent to which smoking and subsequent contact with food by smokers can cause relevant amounts of nicotine to land on the food:
- 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?“.
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 2023.
In this reporting year a total of 423 samples from organic cultivation were analyzed for nicotine. Of these, under partial consideration of drying and processing factors, only 4 samples (0.9 %) contained nicotine > 0.01 mg/kg. This average rate is the lowest among the last years; in 2021 there were 9 of 371 samples (2.4 %); in 2020, 6 of 343 samples (1.8 %); in 2019, 13 of 358 samples (3.6 %); in 2018, 9 of 355 (2.5 %) and in 2017, 19 of 324 (5.9 %).
As in 2021, not a single sample was found to have exceeded the maximum level with verification. In 2020 there was one sample (0.3 %) in violation; in 2019, no samples, in 2018, one sample (0.3 %), and in 2017, four samples (1.2 %) exceeded the limit.
In this reporting year two samples (0.5 %) exceeded the legal maximum level (0.01 mg/kg) within the margin of measurement uncertainty, albeit without verification (flaxseed from India and dried chili flakes of unknown origin). These cases were highlighted in a report drawing attention to the increased residue levels. In 2021 there were three such conspicuous samples (0.8 %), in 2020 one sample (0.3 %) and in 2018 and 2019 two samples each (0.6 % each).
Two further samples (ground cinnamon from Sri Lanka and black tea from India) contained residues in amounts lower than the valid maximum levels, but high enough that they were also highlighted in a report.
It is important to note here that nicotine residues can have various paths of entry that are to be considered and discussed (see Info Box).
An overview of the analyzed samples containing detectable amounts of nicotine, itemized by food group or individual matrix, is presented in the following table.
Matrix / Type of sample |
Amount of nicotine [mg/kg]
|
Maximum residue level [mg/kg]
|
---|---|---|
Parsley, fresh |
0.010
|
0.01*
|
Flaxseed, shelled, fresh |
0.016
|
0.01*
|
Chili flakes, shelled, dried |
0.18
|
0.01*
|
Cinnamon, ground |
0.25
|
4.0**
|
Black tea |
0.32
|
0.6**
|
Trimethylsulfonium cation (trimesium)
In 2022 all 423 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 doesn’t form as a result of an application, however, but rather exists in plant-protection substances as an anti-ion to glyphosate; it is already in a 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 11 samples (2.6 %), compared to 16 of 371 samples (4.3 %) in 2021; 16 of 343 (4.7 %) in 2020; 11 of 358 (3.1 %) in 2019: 6 of 355 (1.7 %) in 2018; and 28 of 324 (8.6 %) in 2017. Two of these (0.5 %) were verified to have exceeded the maximum residue level (under consideration of drying factors). These included red beet powder from Germany and black tea from India. There were no cases of nominal, but unverified, exceedances of the maximum level. The legal maximum level for all of the listed samples and matrices is 0.05 mg/kg.
The previous year (2021) saw 3 of 371 (0.8 %) samples in violation due to analytically verified exceedances of the maximum residue level. In 2020 there were 6 of 343 (1.7 %) such cases, but no anomalies for this substance in 2018 and 2019. In 2017 fully 10 of 324 analyzed samples (3.1 %) were in violation.
The following table shows an overview of the analyzed samples with detected residue amounts, itemized by matrix.
Matrix / Type of sample |
Amount of
trimethlysulfonium cation [mg/kg] |
---|---|
Plant powders, dried: Wheatgrass Acai berries Rosehips Red beet |
0.032 0.080 0.15 1.2 |
Black tea |
0.11
|
Red beets (peeled, boiled; 2x) Flaxseed (shelled) Basil (dried, crushed; 2x) |
0.008 / 0.021
0.021 0.048 / 0.053 |
Sunflower seeds (shelled) |
0.013
|
There are indications 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 an appropriate processing method could reduce the formation of trimesium that occurs via drying. 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. Since the path of entry or the source of the detected residues in these cases is usually not known (similar to the case of nicotine), an organic label isn’t judged as fraudulent. Nevertheless, an indication is made in the report that a documented, intentional application of glyphosate containing plant protection substance would constitute such an offence.
Regardless of the path of entry into the specific food, 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. Investigations into trimesium residues will continue in 2023.
Phosphonic acid, phosphonates and fosetyl
In this reporting year all of the 429 samples (all 423 plus 6 suspicious 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, however, 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. These substances are not 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 I of the new EU Organic Ordinance.
Detected quantities of phosphonic acid can result from the use of a fungicide that contains potassium phosphonate or fosetyl aluminum. The application of a phosphonate-containing fertilizer, a so-called leaf fertilizer, would also be conceivable. Such an application is no longer possible, however, because in the harvest year of 2014, as many as 9 years ago, phosphonate was classified as a fungicide (pesticide substance). 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 time.
The following table shows an overview of the samples with detectable residues, itemized by individual product groups or matrices.
Matrix / Type of sample |
Amount of
phosphonic acid [mg/kg] |
Sum fosetyl [mg/kg]
(Sum of fosetyl and phosphonic acid, expressed as fosetyl) |
---|---|---|
Kumquat Clementine Strawberry Maracuja Ginger, fresh (2 samples) Arugula/ rocket (3 samples) |
0.47
0.23 0.19 0.26 0.12 / 0.21 0.41 / 0.8 / 0.93 |
0.63
0.31 0.26 0.35 0.16 / 0.28 0.55 / 1.1 / 1.2 |
Quinoa, white (3 samples) |
0.31 / 0.56 / 2.6
|
0.42 / 0.7 / 3.5
|
Lentil, dried (brown, red) |
0.22 (brown) / 0.32 (red)
|
0.30 (brown) / 0.43 (red)
|
Wine (white, red) |
0.12 (red) / 0.21 (white)
|
0.16 (red) / 0.28 (white)
|
Pomegranate seed (frozen) |
0.97
|
1.3
|
In 2022 a total of 17 of the 429 samples (4.0 %) contained detectable residues, whereby a significant decrease can be seen over the past few years. The average from this reporting year, however, as in 2021, was less than the already significantly low values from the last few years ((15 of 371 samples (4.0 %) in 2021; 23 of 343 (6.7 %) in 2020; 21 of 358 (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)).
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 amounts of under 0.1 mg/kg to 0.93 mg/kg in an arugula/ rocket sample (origin: Germany) and from 0.97 mg/kg in a sample of pomegranate seeds (frozen, origin: Turkey) to a peak of 2.6 mg/kg in a sample of quinoa (origin unknown).
No residue amounts > 5 or even > 10 mg/kg, which have only seldom and intermittently occurred in previous years, were recorded (as in 2020).
Also of interest is the fact that, in all of the analyzed samples, only residues from phosphonic acid were found, whereas no residues of fosetyl per se were detectable. This points to a likely application of fertilizer containing phosphonic acid or phosphonates, 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), 17 reports were submitted for samples containing residue amounts > 0.1 mg/kg (under consideration of processing factors) in order to highlight this issue among the producers, so that they would attempt to identify the possible paths of entry. This compares to 10 cases in 2021; 22 in 2020; 13 in 2019; 22 in 2018; 21 in 2017; and 43 in 2016.
One of the 429 (0.3 %) analyzed samples ((compared to 0 in 2021; 1 of 343 (0.3 %) in 2020 and 2 of 358 (0.6 %) samples in 2019)) exceeded the valid maximum sum levels for fosetyl (sum of fosetyl and phosphonic acid and their salts, expressed as fosetyl) as stipulated by Regulation (EC) No. 396/2005. In consideration of measurement uncertainty, however, this was not analytically verified. This was a sample of white quinoa (origin unknown) with a residue amount of 3.5 mg/kg (maximum allowed is 2 mg/kg for quinoa).
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 foods such as apricots, peaches, plums, passion fruit, bananas, mangos, carrots, beans, fennel, rhubarb and mushrooms, up to values as high as 1,500 mg/kg for almonds and even 2,000 mg/kg (!) in hops.
Chlorate and perchlorate
In 2022 all 423 samples from organic cultivation were also analyzed for residues of chlorate and perchlorate (an environmental contaminant); see Info Boxes. As with nicotine, fosetyl and phosphonic acid, the unique properties of these two substances preclude their integration in the investigative spectrum of substances analyzed by the QuEChERS multi-method, thus requiring their own processing and analytical methods.
New legal maximum levels for chlorate of between 0.05 and 0.7 mg/kg ((excluding food for babies and young children (0.01 mg/kg)) and first time legally binding levels for perchlorate of between 0.05 and 0.75 mg/kg for matrices other than food for babies and young children (0.01 and 0.02 mg/kg, respectively) have been valid since 1 July 2020.
Background info
Before the afore-mentioned time frame there had been a default maximum level of 0.01 mg/kg for chlorate and various reference values for perchlorate, depending on the matrix. Though not legally binding, these were supposed to guarantee the marketability of the products.
The following table presents an overview of the analyzed samples with detectable amounts, itemized by food group or matrix. For reasons of clarity, only samples containing chlorate and perchlorate > 0.05 mg/kg (lowest valid maximum level at this time, excluding food for babies and young children) are included in the chart.
Among the 16 samples of food for babies and young children that were analyzed, for which significantly lower maximum residue levels are valid (see above), not a single case of detectable residues of these two substances was found. In the previous year (2021) only 1 of 17 analyzed samples contained chlorate in spelt cereal porridge (to be prepared with milk or water) whose amount found in the finished prepared product lay under 0.01 mg/kg. The results of our analyses will be explained in the section following the table.
Matrix / Type of sample |
Quantity of
chlorate [mg/kg] |
Quantity of
perchlorate [mg/kg] |
---|---|---|
Arugula/ rocket Celery Parsley (2 samples) Coriander, fresh Ginger, fresh Basil, dried, crushed (2x) Rosemary, dried, cut Cumin, ground Quinoa, white Linseed Acai berries, dried (powder) |
0.24 0.052 0.19 |
0.15
0.059 / 0.069 0.068 0.11 / 0.15 0.15 0.20 0.070 0.081 |
Quantities of perchlorate were detected in 77 of the 423 (18 %) analyzed organic samples (compared to 16 % in 2021; 20 % in 2020; 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 66 (16 %) samples (compared to 11 % in 2021; 14 % in 2020; 13 % in 2019; 11 % in 2018; 16 % in 2017; 12 % in 2016; 16 % in 2015; 20 % in 2014, and 26 % in 2013).
As 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.
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 the 2023 investigations.
Perchlorate
In this reporting year all of the analyzed samples were evaluated in accordance with the new legal maximum levels for perchlorate established by the EU Contaminants Ordinance (Regulation (EC) No. 1881/2006), valid since July 2020. No samples were registered for an exceedance.
In the previous year (2021), one of the 371 (0.3 %) analyzed samples did exceed the maximum: dried alaria brown algae in powder form. In 2020 two samples of moringa leaf powder (0.6 %) would have also exceeded the maximum levels. However, these samples were collected and analyzed well before the date of validity for these new levels, so they were assessed as having exceeded the then valid EU reference value. These reference values were not legally binding, but would have ensured the marketability of the products
CVUA Stuttgart addressed the issue of perchlorate as many as eight years ago. Since then, the levels of perchlorate residues found in plant-based foods have declined due to a reduction in its application through fertilizers. Nevertheless, the German Federal Institute for Risk Assessment (BfR) recommends a further reduction due to toxicological concerns.
These new EU-wide valid maximum levels, now established and legally binding for a good two years, represent an important step and great success for consumer and health protection. Through its work and analyses, CVUA Stuttgart played a significant role in the introduction of these maximum levels.
Info Box
Perchlorate
Perchlorates are the salts of perchloric acid. They are generally soluble in water and persistent 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 Environmental Agency, the 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 via other components used in 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 also cause the enrichment of perchlorate in soil when used especially in greenhouse cultivation.
Chlorate
A total of 51 of the 423 (12 %) analyzed samples contained chlorate residues > 0.01 mg/kg (7.8 % in 2021; 7.6 % in 2020; 7.0 % in 2019; 3.9 % in 2018; 6.8 % in 2017; 6.2 % in 2016; 11 % in 2015; and 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 2019 samples with verified MRL exceedances (chlorate values > 0.02 mg/kg under consideration of processing and drying factors) were officially reported to be in violation.
At the beginning of 2020, however, the new maximum levels that would become valid in July of that year were already being applied. These lay between 0.05 and 0.7 mg/kg, with the exception of food for babies and young children (0.01 mg/kg). These maximum levels were valid throughout this reporting year of 2022, whereby none of the analyzed samples were found to be in violation due to an exceedance, whether verified or unverified.
In 2021 two samples did present residues above the maximum level, but these were not verified (1x sesame and 1x chlorella algae in powder form, both from unknown origin). For comparison, one sample of chia seeds (origin unknown) was in violation for a verified exceedance in 2020.
Since 2015 there have been new toxicological assessments regarding chlorate residues in food (acute reference dose of 0.036 mg/kg bodyweight and day), published by the European Food Safety Authority (EFSA). Based on these assessments, none of the samples analyzed in 2022 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 protector products (so-called dual-use substances), such as the case of chlorate in food. 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 our red blood cells (formation of methaemoglobin, haemolysis)***. The application of chlorate in the food chain should therefore be further reduced.
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 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)
More notable and interesting findings from reporting year 2022
The following section highlights results from special substances that, due to particularities in their occurence and application or in response to special questions posed, require a separate analysis. It is usually necessary to utilize single methods for such processing and analysis. However, the extra work and costs also yield more consumer protection.
Melamine
Melamine is not a pesticidal substance, but 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 the routine analytical spectrum of substances investigated at CVUA Stuttgart, so every sample is also analyzed for it.
Melamine was detectable in 26 of the 423 (6.1 %) organic samples analyzed in 2022, at levels above 0.01 mg/kg (compared to 4.9 % in 2021; 5.8 % in 2020; and 9.5 % in 2019). Three of these samples (0.7 %) contained amounts above 0.1 mg/kg (0.3 % in 2021; 1.2 % in 2020; and 3.9 % in 2019). This involved one sample each of linseed with 0.36 mg/kg, cucumber with 0.47 mg/kg, and king oyster mushrooms with 1.0 mg/kg. In 2021 there was only one sample of cucumber with 0.47 mg/kg, and 2020 saw 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/ rocket with 0.20 mg/kg. There were no cases of MRL exceedance for melanine in this reporting year, nor for the previous two years. The only exceedance thus far was in a sample of organic potatoes from Germany detected in 2019 with residue levels of 6.3 mg/kg, which was analytically verified.
Melamine can end up in food via, among others, 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.
Herbicidal substances diquat und paraquat
These two substances came onto the market at the end of the 1950s/beginning of the 1960s. They are no longer authorized for use in the EU, however: diquat since 2019 and paraquat since as early as 2007. They are still permitted and in use in many countries outside of the EU, however. For this reason, the main focus of investigations is on goods from third countries as well as on (local) potatoes, since they were allowed earlier in Germany and in the EU. In organic farming, however, neither of these two substances is authorized for use.
In 2022 it was possible for the first time to analyze the herbicidal substances diquat and paraquat on a large, routine scale (in approx.200 organic samples). None of the potato samples investigated in this reporting year was noteworthy in terms of these substances; nothing was found. However, two of the samples from third countries were detected with increased levels of diquat and paraquat (one each): diquat in linseeds from Kazakhstan (residue amount of 0.03 mg/kg) and paraquat in chia seeds from Paraguay (residue amount of 0.095 mg/kg).
The amounts detected in both cases lay significantly and analytically verified above the orientation value for organic goods of 0.01 mg/kg. Both samples were thus deemed fraudulent in view of their organic labeling. The sample of chia seeds also exceeded the valid maximum level for paraquat of 0.02 mg/kg established by Regulation (EC) No. 396/2005, also analytically verified.
Four samples from conventional production were also detected with exceedances of the valid maximum levels for paraquat and reported for violation. These included two samples of chia seeds from Paraguay, and one sample each of sesame and black peppercorns, both of unknown origin. Residues of diquat were also detected in the conventional samples, but these lay below the valid maximum levels.
Inorganic bromide
Increased levels of bromide (degradation product of the fumigant methyl bromide) are sometimes detected in our analyzed samples, both organic and conventional. A fast and effective fumigant, methyl bromide was 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 by 2015. Since 2015 the application of methyl bromide has been extremely restricted worldwide. A reductionary trend in bromide residue amounts is therewith to be expected in the coming years.
Bromide can also occur naturally in soil, however, and there is indication that the naturally occurring quantities of bromide can be higher near the sea or in former marine areas. Italy and other countries often refer to this as a possible source of bromide. 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 only 5 of the 423 analyzed samples (1.2 %) presented with amounts of > 5 mg/kg (4.0 % or 15 of 371 samples in 2021 and 4.4 % or 15 of 343 samples in 2020). These included 2 samples of crushed, dried basil (1 from Germany, 1 origin unknown), 1 sample of guarana powder from Brazil, 1 sample of red beet powder from Germany and 1 sample of millet (origin unknown).
In their reports, CVUA Stuttgart draws attention to detected bromide residues in organic samples that exceed 10 mg/kg (analytically verified exceedances of the orientation value, considering processing/drying factors). All 5 samples with detectable residues of bromide lay below 10 mg/kg, however. In the previous year (2021) there were residue amounts above 10 mg/kg detected in 11 samples; in 2020 there were 4 such samples.
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. In order to protect the goods from storage pests during transport the fumigant hydrogen phosphide is often used in the form of its phosphide salts in sea containers. The salts used in dispensers in solid form 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 expected. Naturally occurring contamination from phosphine is neither known nor proven to date/hitherto. There are discussions, however, regarding the possibility of (cross) contamination from residual dust of previously stored and 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 9 organic samples especially for residues of the fumigant hydrogen phosphine (sesame, nuts, lentils and rice). From 2017 to 2020 phosphine residues were found mainly in dried legumes (lentils) and cereals (rice).
None (0 %) of the analyzed samples contained residues of phosphine (compared to 38 % in 2021; 32 % in 2020; 33 % in 2019; 14 % in 2018; and 12 % in 2017). Residue levels in previous years were usually very low, less than 5 µg/kg (0.005 mg/kg). The lowest maximum level for phosphine (10 µg/kg) established by Regulation (EC) No. 396/2005 was thereby significantly undercut.
In 2022 as well as in the 2 previous years there were no violations for organically grown samples, either due to an MRL exceedance or to fraudulent organic labeling. In 2019, however, one sample of lentils from Turkey was conspicuous for constituting a violation.
Eight samples from conventional production were also analyzed for phosphine in 2022 (lentils, beans and chick peas). Residues were detected in 3 samples: 1 sample of red lentils from Turkey with < 0.005 mg/kg and 1 sample each of yellow lentils from Turkey and chick peas from Mexico containing > 0.01 mg/kg, which is above the legally valid maximum level.
Ethylene oxide and 2-chloroethanol
Investigations, results and background information on this topic can be found in reports published by CVUA Stuttgart in the years 2020 and 2021 (10 Dec. 2020, 28 July 2021 and 17 Aug. 2021) at the following website links: Sesame seeds, Plant powder and nutritional supplements, Instant noodles.
In this reporting year a total of 43 samples of organic produce were analyzed for residues of ethylene oxide and its degradation product 2-chloroethanol. Only 1 of these samples (2.3 %) contained residues of 2-chloroethanol (6.7 % or 9 of 134 samples in 2021), whereas ethylene oxide was not detected at all. This was a sample of freeze-dried acai berries in powder form, containing 0.38 mg/kg (equates to 0.21 mg/kg calculated as ethylene oxide). The valid maximum level of 0.02 mg/kg in accordance with Regulation (EC) No. 396/2005 was exceeded without analytical verification when taking drying factors into consideration. Toxicological reference values were neither exhausted nor exceeded here. However, since the orientation value of 0.01 mg/kg for organic products was exceeded and the substance is not permitted for use in organic farming or organic foods, the organic labeling was deemed violatory.
In the previous year (2021) were nine organic samples with detectable residues. These included the following products: vegan soy-based wiener substitute, barley grass powder, milk thistle powder, turmeric powder, red maca root powder and moringa oleifera leaf powder (4x).
The detected amounts of 2-chloroethanol ranged from 0.065 mg/kg in a vegan soy-based wiener substitute to peak values of 410 mg/kg, 733 mg/kg and 1,030 mg/kg in moringa oleifera leaf powders. Ethylene oxide itself was not detectable in any samples. Five of these samples exceeded, analytically verified, the valid legal maximum levels according to Regulation (EC) No. 396/2005. They were all judged to be unsafe foods due to the exhaustion of the toxicological reference values (4 samples of moringa oleifera leaf powder were judged to be a health hazard and 1 sample of barley grass powder was deemed unsuitable for consumption).
Authors
Marc Wieland, Ellen Scherbaum and Kathi Hacker, CVUA Stuttgart
Translated by: Catherine Leiblein