Examination of plant protection product samples

Transcription

1 Examination of plant protection product samples BVL, 18. April 2017 Seite 1 von 10

2 Overview In 2016, 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 and clarifying issues related to import controls 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 non-compliance) 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') participating in collaborative trials for developing methods and for international standardisation as well as proficiency tests for investigating the quality of the analysis results Contact address: Bundesamt für Verbraucherschutz und Lebensmittelsicherheit Dienststelle Braunschweig Messeweg 11/ Braunschweig Referat 206 Labor für Formulierungschemie Telephone: Picture Credits: BVL/Gloger BVL, 18. April 2017 Page 2 of 10

3 Table of contents 1 Monitoring the composition and physical, chemical and technical properties of plant protection products as part of the Plant Protection Control Program Plant protection products containing certain active substances (planned samples)... 4 Results of the examinations Samples in cases of suspected non-compliance... 5 Results of the examinations Table showing analyses and results Examining the properties of plant protection products in the context of the authorisation procedure for plant protection products... 8 Results of the examinations Reassessing identity in the approval procedure for parallel trade with plant protection products... 9 Results of the examinations Ring trials, interlaboratory studies Summary BVL, 18. April 2017 Page 3 of 10

4 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 2016 on the composition of plant protection products on the market containing the active substances azoxystrobin or nicosulfuron. It was planned to reassess authorised original products as well as plant protection products for parallel trade. 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 impurities such as (Z)-Azoxystrobin and toluene foreign substances (using a multi-method) content of co-formulants such as antifreeze density as a significant identity criterion appearance/colour homogenisability dispersion stability wet sieve test Out of a total of 187 planned samples examined, 22 samples were from parallel trade products (11.8%). In 2015, parallel trade made up for 5.9 % of domestic sales. BVL, 18. April 2017 Page 4 of 10

5 Results of the examinations In 4 out of the 111 examined plant protection products containing azoxystrobin, the active substance content was above the permissible FAO/WHO tolerance range. It must be mentioned, however, that the azoxystrobin containing samples in question are plant protection products in very small containers for use in private gardens. Additionally, in one out of the 111 examined plant protection products containing azoxystrobin, the coformulant content was found to be below the tolerance range. When examining the homogenisability of liquid plant protection products (see BVL s homepage - PlantProtectionProducts / ProductChemistry / BVL laboratory for formulation chemistry), it was found that despite intensive efforts a number of samples from one plant protection product containing nicosulfuron could not be homogenised. For all the above mentioned deviations or other conspicuous findings, consultation procedures have been started, the results of which were not yet available at the time this report was written. On the basis of the analysed parameters, the composition of 179 of the 187 planned samples examined was in accordance with the legal prescriptions (see tables 2 and 3). This is a deficiency rate of 4.3 % (see table 1). The ratios stated in table 2 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 there are specific grounds for checking at wholesale, retail, at the production level or when considering complaints and during these controls the federal states find conspicuous results or irregularities, then, in the context of official sampling, suspicious samples can be taken and be sent to the BVL for examination. In 2016, a total of 59 suspect samples were analysed at the laboratory for formulation chemistry. Those plant protection products contained 32 different active substances or active substance variants: Acetamiprid, azoxystrobin, benalaxyl-m, bentazone, bromoxynil, CCC, chlorantraniliprole, chlorpyrifos, clopyralid, dicamba, difenoconazole, epoxiconazole, ethephon, fenpropimorph, fluopyram, fluroxypyr, folpet, glyphosate, Iodosulfuron, isopyraxam, ioxynil, kresoxim-methyl, mesosulfuron, metaldehyde, metamitron, metribuzin, nicosulfuron, prothioconazole, quizalofop-p, tebuconazole, thiacloprid and tribenuron methyl. In particular cases, it was decided which parameters should be examined in order to clarify the suspicious circumstances. In most cases this involved active substance contents, impurities and foreign substances and for liquid formulations homogeneity and 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 colour, emulsion stability, ph-value, surface tension, suspensibility, dust formation, wet-sieve test or persistent foaming were examined. Moreover, the majority of samples was examined by using a GC-MS screening method in order to see whether they contain other substances. BVL, 18. April 2017 Page 5 of 10

6 One of the submitted suspect samples was labelled as technical calcium carbide. As the laboratory for formulation chemistry does not dispose of the equipment and experience necessary in order to analyse the sample, it has been sent to the Chemical Institute of Pforzheim. Despite all possible sorts of examinations, no clear conclusions can be drawn on whether the sample contains calcium carbide or aluminium carbide. However, the complaint was justified since the technical active substance was labelled and sold as a plant protection product. The analyses carried out on this do not appear in table 2 and table 3 below. Results of the examinations In 2016, a total of 9 suspect samples were examined due to crop damage. Among them was also one plant protection product having a total of 3 samples. However, the results of these examinations did not contain any evidence regarding the cause of the crop damage. In the case of one sample, the persistence of foaming was much higher than that which is acceptable according to FAO/WHO Manual (2010). But this cannot explain the crop damage. In one of the 6 examined samples it was claimed that an active substance content was too low. If this is the reason leading to a reduced efficacy should be clarified elsewhere. The 5 other samples showed no inadmissible deviations from the reference values. In total, 11 samples of authorised plant protection products were examined for suspected non-compliance with the authorisation requirements. This suspicion was confirmed in one case, the other samples did not show signs of a defective composition. 18 samples have been taken from plant protection products with a parallel trade permit because of suspicion of defective compositions. The examinations have shown that the initial suspicion was confirmed in 11 cases. Deviations were mainly detected in co-formulant substance contents. However, in one case the foam was also much higher than the acceptable tolerances given in the FAO/WHO Manual from In the course of import inspections in the port of Hamburg, 18 samples from plant protection products have been taken and submitted to the BVL for examination. None of the samples had an authorisation number or GP-number indicating their approval for parallel trade. This is why no control of marketability but only examinations were carried out to determine whether the active substances indicated on the delivery documents (partly also indicated with their quantity) were correct and whether the samples contained (eco) toxicological relevant substances. The examination results were not evaluated. One suspect sample without an authorisation number or GP-number was submitted to the BVL and could not, therefore, be categorized like the above mentioned cases. According to the product name, an authorisation number was assumed and the examination results were referred to the reference values of the corresponding authorisation documents. One deviation was found in the field of co-formulants, so that the sample was not only unacceptable because of its missing authorisation number and GP-number but also from an analytical point of view, provided that the assumption based on the reference values and authorisation number is correct. One sample was labelled as a product for snails but, again, did neither have an authorisation number nor a GP-number. This sample was examined for the presence of molluscicide active ingredients and other substances. No indication was found of any such active substances. BVL, 18. April 2017 Page 6 of 10

7 1.3 Table showing analyses and results Table 1 shows how the 246 inspected plant protection product containers are distributed amongst the different kinds of samples. Planned samples containing the active substances azoxystrobin and nicosulfuron represent the largest percentage of samples. 59 plant protection products were examined due to suspicious or concrete circumstances, except that one of the samples has been submitted to an external contractor for examination. Table 2 provides a summary of the analyses carried out and the parameters which caused objections. 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 ** 23 (9,4 %) 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) - due to damage/reduced efficacy - suspicion of a defective composition of authorised products - suspected illegal (parallel) trade - in the context of import controls (port) - others, for example plant strengtheners ** * 2 + 1** 8 (4,3 %) 8 (4,8 %) 0 (0,0 %) 15 (25,9 %) 2 (22,2 %) 1 (9,1 %) 11 (61,1 %) not relevant* 1 (50 %) * These samples were analytically examined to see whether the active substances and toxicologically relevant components indicated on the delivery documents have been included in the product. They were not examined for their marketability. ** Sample has been examined by an external contractor, objection due to labelling, was not taken into consideration when calculating the percentage of objections. Table 2: Analyses and detected deviations from authorisation data for samples from the Plant Protection Control Program in 2016 Analysis parameters Planned samples Samples in cases of suspected non-compliance Analyses Irregularities Analyses Irregularities Type of active substance Content of active substance Impurities/ foreign substances Co-formulants Physical, chemical, technical properties Homogenisability Screening (GC/MS) Screening (HPLC/UV) In total qualitative and quantitative determination of the active substance count as one determination per sample 2 some samples show deviations in two test parameters BVL, 18. April 2017 Page 7 of 10

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 requests 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 examination in the laboratory for formulation chemistry 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/WHO criteria or the existing specifications. In 2016, 32 samples were received in connection with the authorisation procedure according to Article 28 of Regulation (EC) No 1107/2009, of which 9 samples had been examined by the end of the year. Furthermore, 15 samples from applications in 2015 were examined. A total of 454 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 109,2012) 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) dust content (CIPAC MT 171) flowability (CIPAC MT 172) wettability (CIPAC MT 53.3) degree of dissolution and solvent stability (CIPAC MT 41 and MT 179) BVL, 18. April 2017 Page 8 of 10

9 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 physical, chemical and technical parameters were then determined. In addition, the active substance from some samples were qualitatively and quantitatively 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 2016 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. 490 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. Samples were examined for the following parameters, according to the relevant issue: density contents of selected co-formulants (e.g. solvents) active substance contents The compositions sent in from the Member States according to Article 52 of Regulation (EC) No 1107/2009 do not always reflect the current composition of the goods available on the market there. The various compositions originate from different authorisation modalities in the Member States with regard to changes of formulation. Inaccurate designations for some co-formulants also gave rise to analysis. A total of 2 samples were examined. 6 analyses were carried out. Results of the examinations On the grounds of the analyses, all open issues could be clarified. In all cases, an approval for parallel trade could be issued on the basis of the results. BVL, 18. April 2017 Page 9 of 10

10 4 Ring trials, interlaboratory studies In 2016, the laboratory took part in a proficiency test by the Association of American Control Officials (AAPCO) as a means of monitoring its own efficiency. 3 plant protection formulations were examined for their content of 4 active substances. The laboratory achieved impeccable quality for all of the parameters (z-scores ranging between 0.08 and 1.29). As there was no provider for covering the proficiency tests planned for 2016, the tests were carried out in cooperation with the laboratory AGES (Austria) and the laboratory Agroscope (Switzerland). Within the framework of these examinations, 4 samples have been analysed regarding their colour and surface tension, 2 samples have been tested for their dust content and one sample each for emulsion stability, dispersion stability, wet sieving and wettability. For all samples comparable results were obtained between the laboratories. Furthermore, the laboratory participated in 5 ring trials on the development of methods in the context of CIPAC (Collaborative International Pesticides Analytical Council), DAPA (German Speaking Working Group for PPP Analysis) and DAPF (German Speaking Working Group for PPP Formulations). Depending on the problem, the 20 submitted samples were examined for their active substances like D-tetramethrin (in 5 samples), mancozeb (in 5 samples) and flupyradifurone (in 7 samples), but 3 samples were also analysed for their spray rate. 5 Summary In table 3, the examinations of the plant protection product containers inspected in 2016 are grouped in relation to various tasks. Furthermore, where possible, the ratio of irregularities is stated. The suspect sample which has been examined by an external contractor is not listed in the table. Table 3: by the laboratory for formulation chemistry, Unit 206 (BVL), in 2016 Task Number of samples Irregularities (concerning samples) Analyses Planned samples (Plant Protection Control Program) Samples in cases of suspected noncompliance (Plant Protection Control Program) Authorisation procedure for plant protection products open 454 Approval procedure parallel trade Ring trials, proficiency tests 33 not relevant 40 total BVL, 18. April 2017 Page 10 of 10