Examination of plant protection product samples. Annual report 2014

Transcription

1 , Examination of plant protection product samples Annual report 2014

2 Contact address: Federal Office of Consumer Protection and Food Safety (BVL) Dienststelle Braunschweig Messeweg 11/ Braunschweig Referat 206 Labor für Formulierungschemie Telephone: April 2015

3 Page 3 Examination of plant protection product samples Annual report 2014 In 2014, plant protection products were examined experimentally in the laboratory for formulation chemistry, Unit 206 ("Product Chemistry and Analytical Methods") in the light of the following tasks: monitoring the composition and properties of plant protection products on the market in the context of the Plant Protection Control Program of the federal states and federal government (examination of planned samples and samples in cases of suspected noncompliance) investigating the properties of plant protection products in the context of the authorisation procedure for plant protection products according to Regulation(EC) No 1107/2009 investigating the composition and properties of plant protection products in the approval procedure for parallel trade according to Article 52 of Regulation (EC) No 1107/2009 and Article 46 German Plant Protection Act ('PflSchG') compiling official reports for court procedures participating in collaborative trials for developing methods and for international standardisation as well as proficiency tests for investigating the quality of the analysis results 1 Monitoring the composition and physical, chemical and technical properties of plant protection products as part of the Plant Protection Control Program The plant protection services of the federal states take samples of plant protection products on the market which are then analysed by the BVL. The BVL examines them to see whether the content of the active substance, co-formulants, impurities and foreign substances and the physical, chemical and technical properties correspond with the data set at the time of authorisation, or approval for parallel trade, concerning their composition and any conditions which they may have to fulfil. In this way, plant protection products which are on the market are examined for consistency with authorisation or for approval for parallel trade as well as for quality deficiencies resulting from production or storage. 1.1 Plant protection products containing certain active substances (planned samples) As far as market inspections are concerned, it was decided that spot tests should be carried out in 2014 on the composition of plant protection products on the market containing the active substances flufenacet or boscalid. Moreover, it was agreed to examine a plant protection product containing terbuthylazine and a product containing Fluroxypyr-1-Methylheptyl ester,

4 Page 4 which was considered to be conspicuous in earlier annual monitoring exercises. It was planned to reassess authorised original products as well as plant protection products intended for parallel trade containing the active substances flufenacet or boscalid. Inspections of the plant protection product containing terbuthylazine and the product containing Fluroxypyr- 1-Methylheptyl ester are limited to the original products that previously turned out to be conspicuous. In the context of these inspections, samples of plant protection product packaging for wholesale and retail use were taken, sent to the Unit, "Product Chemistry and Analytical Methods", at the BVL, and then examined in the laboratory for formulation chemistry. Depending on their formulation, the planned samples were examined for the following parameters: active substance content content of the co-formulant substance naphthalene content of the relevant impurity atrazine appearance/colour homogeneity for liquid formulations: density as a significant identity criterion for emulsifiable concentrates: emulsion stability as a significant criterion Out of a total of 199 planned samples examined, 7 samples were from parallel trade products (3.5 %). In 2013, parallel trade made up for 7.1 % of domestic sales. Results of the examinations The 109 examined plant protection products containing flufenacet as well as the 7 examined plant protection products containing Fluroxypyr-1-Methylheptyl ester showed neither deviations in their active substance content, in the contents of the analysed co-formulants and impurities nor in the physical, chemical and technical parameters examined. Out of a total of 69 examined plant protection products containing boscalid, one sample showed a deviation in the active substance content. Another plant protection product sample containing boscalid could not be homogenised, although the procedure was performed according to BVL publication homogenisability of plant protection products (BVL-Homepage > Pflanzenschutzmittel > Aufgaben im Bereich Pflanzenschutzmittel > Produktchemie > Labor für Formulierungschemie). Since representative sampling from the packaging was not possible, no further examinations were carried out for this sample. Among the 14 examined plant protection products containing terbuthylazine, one sample showed a deviation in contents of the active substance impurity atrazine.

5 Page 5 On the basis of the analysed parameters, the composition of 196 of the planned samples examined was in accordance with the legal prescriptions (see tables 1 and 2). This is a deficiency rate of 1.5 % (see table 1). The ratios stated in table 1 do not have any statistical weight due to the small number of samples used as a basis; they merely depict a trend. 1.2 Samples in cases of suspected non-compliance If the federal states ascertain apparent non-compliance or irregularities at wholesale, retail or production level during specific controls or when investigating complaints, samples can be taken in conjunction with official monitoring on the grounds of suspected non-compliance and sent to the BVL for examination. In 2014, a total of 15 samples in cases of suspected noncompliance were analysed at the BVL. Those plant protection products contained 15 different active substances: thiacloprid, ethephon, cyproconazole, propiconazole, clomazone, imidacloprid, chlorsulfuron, thifensulfuron, glyphosate, dithianon, prohexadione (as calcium salt), folpet, pendimethalin, flufenacet and chlormequat chloride. In each single cases it was decided which parameters should be examined in order to clarify the suspicious circumstances. In most cases this involved contents of active substances, impurities and foreign substances and for liquid formulations density. Depending on the issue, further parameters such as the content of certain co-formulants, for example solvents and physical, chemical and technical properties such as emulsion stability, ph-value, surface tension, suspensibility or persistent foaming were examined. Results of the examinations 10 of the 15 examined plant protection products showed irregularities. One plant protection product was examined for an unknown crop intolerance occurring during the application. When compared to the authorisation requirements, deviations were found in the composition. Whether these deviations were responsible for the detected crop intolerance could not yet be determined. Another plant protection product has been examined because of damage to bees. There was no evidence of inadmissible deviations from the authorisation requirements. 5 authorised products were submitted to the BVL due to suspected irregularities in their composition. Those samples were examined for their active substance contents and their contents of impurities. Products containing captan were examined for impurities through folpet. One herbicide was examined for impurities with other herbicides and two further plant protection products were examined for impurities with chlorpyrifos and iprodione. One of the plant protection products examined was shown to be not admissible for placing on the market because its active substance content was too high.

6 Page 6 A sample taken in case of suspected non-compliance concerned a product which was intended for parallel trade and has been seized from commercial establishments. The product was not marketable because the GP-number printed on the product was no longer valid. This sample was found to have an excessive content of the relevant impurity with 1,2- dichloroethane. A set of 6 plant protection products and one further plant protection product were sent in for examination because they were neither authorised nor approved in Germany. Since those 6 plant protection products were originally from Poland, the polish authorisation authority provided the composition registered in their country. In one case the plant protection product could not be homogenised, that is why an examination of the sample was not possible. The examinations of two samples showed no inadmissible deviations from the declared active substance contents. The maximum limits for the impurities examined were also observed. Though the three samples showed no deviations from the declared active substance contents, unduly high contents of different foreign substances and a few deviations regarding the co-formulants and the physical, chemical and technical parameters were found. No deviations were found in the plant protection product which was sent in separately, the active substance content corresponded to the information on the packaging. Overall, however, all 7 samples must be classified as non-marketable, as no authorisation or parallel trade permit has been granted to them. 1.3 Table showing analyses and results Table 1 shows how the 214 inspected plant protection product containers are distributed amongst the different kinds of samples. Planned samples containing the active substances Fluroxypyr-1-Methylheptyl ester, flufenacet, boscalid or terbuthylazine represent the largest percentage of samples. 15 plant protection products were examined due to suspicious or concrete circumstances. Table 2 provides a summary of the analyses carried out and the parameters which caused objections.

7 Page 7 Table 1: Product quality inspections in summary of samples with irregularities concerning the composition and the nature of the product Inspections (amount) Objections (number, percentage) Number of inspected plant protection products, total (6.1 %) Share of systematic inspections (planned samples) - share of authorised products - share of products intended for parallel trade share of inspections for specific reasons (suspect samples) - share due to damage - including suspicion of the defective composition of authorised products - share of suspected illegal (parallel) trade (1.5 %) 3 (1.6 %) 0 (0.0 %) 10 (66.7 %) 1 (50.0 %) 1 (20.0 %) 8 (100 %) Table 2: Analyses and detected deviations from authorisation data for samples from the Plant Protection Control Program in 2014 Analysis parameters Planned samples Samples in cases of suspected non-compliance Analyses Irregularities Analyses Irregularities Type of active substance Content of active substance 1 Impurities/ foreign substances Co-formulants Physical, chemical, technical properties Homogenisability Screening (GC/MS) in total a qualitative and quantitative determination of the active substance counts as one determination per sample

8 Page 8 2 Examining the properties of plant protection products in the context of the authorisation procedure for plant protection products The processing of applications for authorisation according to PflSchG or Regulation (EC) No 1107/2009 also involves the physical, chemical and technical evaluation of plant protection products. In case of applications for the authorisation of new formulations for which Germany is the Rapporteur Member State, the BVL requested samples in order to supplement assessment with an experimental examination. Samples are also requested for plant protection products whose formulation has been changed or for applications for renewed authorisation if the last laboratory examination lies way back in the past. The examinations are carried out for several reasons: To re-examine the applicant's data. Deviations between the values measured in the laboratory at the BVL and the values from the studies submitted by the applicant are tolerated to a certain extent. To re-examine storage stability and the safe use of the formulations To re-examine to what extent the formulations correspond to the general FAO criteria or the existing specifications In 2014, 72 samples were received in connection with the authorisation procedure according to Article 28 of Regulation (EC) No 1107/2009, of which 36 samples had been examined by the end of the year. Furthermore, 12 samples from applications in 2013 were examined. A total of 859 analyses were carried out. A selection of the following physical, chemical and technical properties typical for formulations was examined, depending on the type of formulation: surface tension (OECD Test 115, 1995) ph value (CIPAC MT 75.3, 2000) density (OECD Test 109,1995) emulsion stability (CIPAC MT 36.3, 2003) persistent foaming (CIPAC MT 47.2, 1995) particle size distribution (laser granulometer) pourability (CIPAC MT 148) suspensibility (CIPAC MT 184, 2003) bulk/apparent volume (CIPAC MT 169,186) dust content (CIPAC MT 171) flowability (CIPAC MT 172)

9 Page 9 wettability (CIPAC MT 53.3) degree of dissolution and solvent stability (CIPAC MT 41 and MT 179) attrition (CIPAC MT 178.2) dispersion stability (CIPAC MT 180) flashpoint (EG 9) colour (BVL_P-IN01)) For most of the examined samples, a selection of the parameters stated was determined before and after a storage test at increased temperatures (CIPAC MT 46.3). A storage test was also carried out at low temperatures (according to CIPAC MT 39.3) for liquid samples and the physical, chemical and technical parameters were then determined. Results of the examinations The results of the examination are reported to the in-house person who requested them and who is concerned with the assessment in the context of the authorisation procedure for plant protection products. The assessment is always carried out with a time lag, so that an evaluation regarding the deviations of the results found in 2014 compared with the studies submitted in the context of the authorisation procedure has not yet been performed. 3 Reassessing identity in the approval procedure for parallel trade with plant protection products Parallel traders can submit applications according to Article 52 of Regulation (EC) No 1107/2009 for an approval for parallel trade. The approval allows the approval holder to market identical plant protection products from EU Member States in Germany. 784 approvals for parallel trade were applied for in In processing an application, the BVL can request a sample of the product which is to be imported in order to examine its identity. However, in 2014 no examination was commissioned.

10 Page 10 4 Official expert opinions for law courts on the composition of plant protection products The market for plant protection products is also increasingly being observed by authorisation holders. Samples are taken and examined as a part of these observations. On the grounds of the results, parallel traders are often sued by authorisation holders. In these civil law cases, the BVL is asked by the competent courts to compile official expert opinions on the composition of the samples concerned. The parameters examined depend greatly on the issues specified by the court and apart from the examination of the active substance content can also include an examination of the content of co-formulants, relevant impurities or physical, chemical and technical properties. In 2014, 4 samples and a total of 16 parameters were examined by the laboratory for formulation chemistry for expert opinions for law courts 5 Proficiency tests, collaborative trials In 2014, the laboratory took part in a proficiency test by the Association of American Control Offices (AAPCO) as a means of monitoring its own efficiency. 4 plant protection formulations were examined for their content of 5 active substances. The laboratory achieved impeccable quality for all of the parameters (z-scores ranging between and 1.075). Furthermore, the laboratory for formulation chemistry took part in an arbitral analysis by the Federal Agency for the Safety of the Food Chain (FASFC). A formulation was examined for its active substance content as well as ph-value, persistent foaming and dilution stability. Here, too, the laboratory achieved impeccable quality for all of the parameters (z-scores ranging between and 0.27).

11 Page 11 6 Summary In table 3, the examinations of the plant protection product containers inspected in 2014 are grouped in relation to various tasks. Furthermore, the percentage of irregularities is stated. Table 3: Examination of plant protection product samples by the laboratory for formulation chemistry, Unit 206 (BVL), in 2014 Task Planned samples (Plant Protection Control Program) Samples in cases of suspected non-compliance (Plant Protection Control Program) Authorisation procedure for plant protection products Number of samples Irregularities (concerning samples) Analyses open 859 Approval procedure parallel trade Official expert opinion 4 no information 16 Proficiency tests, collaborative trials 5 not relevant 9 Total ,876