3.D.f - Agriculture Other including use of pesticides

Last updated on 12 Feb 2020 11:37 (cf. Authors)

Background

Hexachlorobenzene (HCB) is one of the listed persistent organic pollutants covered by the the Aarhus Protocol on Persistent Organic Pollutants from 2009, Annex III [13], the Stockholm Convention [14] and Directive 2016/2284 (NECD), Annex I from 2016 [21]. These conventions and directives oblige parties to reduce their emissions of dioxins, furans, polycyclic aromatic hydrocarbons (PAHs) and hexachlorobenzene (HCB) below their levels in 1990.

In Germany the application of HCB as a pesticide, in a pure form, has been prohibited since 1977 and thus no HCB emissions were reported before 2015.
However, HCB can occur as an impurity in active substances e.g.:

  • Lindane (gamma-hexachlorocyclohexane, γ-HCCH),
  • DCPA (Dimethyl tetrachloroterephthalate also known as chlorthal-dimethyl or Dacthal),
  • PCP (Pentachlorphenol),
  • Atrazine (2-Chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine),
  • Simazine (2,4-Bis(ethylamino)-6-chloro-1,3,5-triazine),
  • Propazine (2,4-Bis(isopropylamino)-6-chloro-1,3,5-triazine) and PCNB (Pentachlornitrobenzol also known as quintozine).

Further active substances are chlorothalonil (fungicide), tefluthrin (insecticide) and picloram (herbicide). These active substances are continued to be used in approved pesticides in Germany (cf. Table I, Pesticides). Tefluthrin is not emission relevant due to the application method. The pesticide is applied on seed in closed storage buildings (communication by Syngenta Agro, 2015 [16]). Thus, it is not considered in the amount of reported HCB emissions.

Table 1a, Chlorothalonil & Table 1b, Picloram: Overview of plant protection products and their trade names, chemical agents, intended applications and approval numbers; last revision, 2020

IIR_2020_3.d.f_tab1a.PNG
IIR_2020_3.d.f_tab1b.PNG
//Source: https://apps2.bvl.bund.de/psm/jsp/index.jsp, https://www.proplanta.de/Pflanzenschutzmittel///

HCB has never been contained in co-formulants of approved pesticides (communication of the Federal Office of Consumer Protection and Food Safety (BVL, 2015) [23].

In the past, some applicants listed maximum HCB concentrations in technical active substances in certain lindane-containing substances. The concentrations given amounted to ≤ 0.1 g/kg, a level oriented to the detection limits of the analysis method used at the time. Substances conforming to that maximum concentration were approved only through 1989 or 1990 (in one case, through 1995). Obligations to report substance quantities sold did not take effect until 1998. For the other relevant active substances, the BVL has no information on HCB as an impurity.

Methodology

The emissions were calculated in keeping with the method proposed in the EMEP (2019) [32] (-3Df/3I-5, chapter 3, Tier 1 approach).

Epest = Σmpest_i • EFpest_i

To estimate the emission of HCB which is present as an impurity, an impurity factor (IF) has to be considered in the calculation:

Epest = Σmpest_i • IFj,i • EFpest_i
where:
Epest = total HCB emission of active substance (in mg a-1, unit conversion reported in kg a-1),
mpest = mass of individual active substance applied (kg a-1),
IFj,i = impurity factor of the jth active substance in the ith active substance (mg kg-1)
EFpest= EF for individual active substance (volatile fraction of applied amount of the active substance).

A modeled emission factor is used for Germany (see description of Emission factors). According to the definition of the Tier 2 Approach1 (EMEP Guidebook 2019 [32]) the method can be described as Tier 2.

Activity data

As activity data, domestic sales of pesticides with the active substances chlorothalonil and picloram compiled by the BVL (BVL, 2019 [24]) were used (reports pursuant to § 64 of the Plant Protection Act (PflSchG, 2012 [15]); cf. Table II, domestic sales.

Table II: Published data on domestic sales of active substances, in t/a, 1990 - 2018, [33]

IIR_2020_3.d.f_tab2.PNG

The quantities sold domestically are assumed to be equivalent to the quantities used. The specific sales data used in the calculation are considered to be business and operational secrets and thus have to be kept confidential.

HCB Impurities

The HCB quantities are calculated in light of the maximum permitted concentrations of HCB impurities established by legal acts of the EU2. The approach is a highly conservative one that probably overestimates the actual emissions. The BVL has no information regarding the actual concentrations of impurities, either past or present, in pesticides placed on the market.

Chlorothalonil:
Before 2006 there was no legal regulation in Germany on the maximum content of HCB in the active ingredient chlorothalonil. However, with the implementation of Directive 91/414/EEC [25], manufacturers had to analyse their technical active substance for possible relevant impurities and, where appropriate, indicate a maximum level. These maximum levels had to be maintained. Information about the levels specified for chlorothalonil for the years 1990 and 1999 for Germany are not known. As described in the FAO specification (2015, p. 49, [26]) Chlorothalonil was reviewed by IPCS (INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY) in the Environmental Health Criteria (EHC) series in 1996. The limit for HCB in the FAO specification in 1998 for chlorothalonil was 0.3 g/kg and manufacturer stated in that report that the company had improved the manufacturing process (see FAO Specification, 2015, p. 51, [26]) .
Thus, a maximum HCB concentration of 300 mg/kg (IPCS, 1996 [30]) is considered for the years 1990 until 1999 for Germany.

Directive 2005/53/EC [18], which entered into force on 1 March 2006, established a maximum permitted HCB concentration of 10 mg/kg in chlorothalonil as a technical active substance. Due to a review by the FAO 288/2005 (see FAO 2015, p.22 and p. 51 [26]) and taking into account the results of batch samples testing the impurity the max. concentration was raised again up to 0.04 g/kg. Thus, the standard was raised to 40 mg/kg in Directive 2006/76/EC [19].

For the years as of 2000, the specified maximum HCB concentrations in chlorothalonil differ considerably from pesticide to pesticide – in some cases despite the EU-regulation, the values differ from year to year for the same pesticide. For the year 2000 an interim value was calulated by linear interpolation. (170 mg/kg). For the years 2001 to 2004, the value of 40 mg/kg is used.

The quantities of pesticide active substances sold, and reported pursuant to Art. 64 Plant Protection Act [15] were used as a basis for deriving a weighted average for the maximum concentrations for 2000, 2005, 2010 and 2013 (cf. Table IV, concentrations of impurities). The average was used to calculate the relevant HCB quantities for the period between 2005 and 2008. For the later years starting from 2009 onwards the information on the maximum concentration of 10 mg/kg is assumed which is indicated by the authorisation holders (Syngenta Agro, 2015 [16]).

Picloram: For picloram, a maximum concentration of 50 mg/kg has been specified for some pesticides. Relevant pesticides were introduced in Germany beginning in 2006. Picloram was added to Annex I with the Commission Directive 2008/69/EC [20] and the HCB impurity is still set to 50 mg/kg (FAO, 2012 [27]).

Lindane: The HCB quantities in lindane were determined with the help of historically reported lindane-quantity data (cf. Table III) of the former former Federal Biological Office for Agriculture and Forestry (Biologische Bundesanstalt für Land- und Forstwirtschaft; BBA), Institute of Pesticide Technology Assessment (Institut für Folgenabschätzungen im Pflanzenschutz, Kleinmachnow). Those data are based on information that producers provided voluntarily. For the years after 1997 no data are available because the application of Lindan was phased out in 1998.

Table III: Domestic sales of Lindane, in t/a

IIR_2018_3.d.f_tab3.PNG

For lindane, a maximum concentration of 100 mg/kg was specified for the years 1990 through 1994. For the years after 1994 a lower concentration (50 mg/kg) was assumed which is based on compiled information of Bailey (2001) [22] (cf. Table IV).

Table IV: Maximum concentrations of HCB impurities in relevant active substances, in mg per kg

IIR_2020_3.d.f_tab4.PNG

In recent years, the total HCB quantities in pesticide active substances (cf. Table V) have been affected primarily by sales of chlorothalonil.

While this results from the large quantities of chlorothalonil-containing pesticides sold, it is also due to the high chlorothalonil concentrations in such pesticides and to the high permitted maximum HCB concentrations (0.3 g/kg), in chlorothalonil as a technical active substance, that applied prior to 2000. Due to the revised data, changes in HCB quantities occur.
The maximum HCB quantity for picloram, in the period under consideration, were lower, respectively, than the relevant quantities for chlorothalonil. For this reason, fluctuations in sales of picloram have very little impact on maximum HCB quantities.

Table V: Maximum HCB quantities in domestically sold active substances in pesticides [kg] from 1990 until 2018

IIR_2020_3.d.f_tab5_1990-1999.PNG
IIR_2020_3.d.f_tab5_2000-2009.PNG
IIR_2020_3.d.f_tab5_2010_2018.PNG

Emission factor

The HCB emission factor was modeled by using the Pesticide Leaching Model (PELMO 3.31) which is also used for the European registration process of pesticides. The one-dimensional pesticide leaching model has been extended to predict the pesticide volatilisation after agricultural applications under field conditions (Ferrari et al., 2005 [28]) however, it is also able to calculate the behaviour of impurities in the products. The model was developed by the Fraunhofer Institute for Molecularbiology and Applied Ecology (IME).

Due to its volatility behaviour in the presence of water vapor even at low temperatures, ambient HCB is usually found in the vapour phase and appears to volatilize from plant and soil surfaces during the first 24 hours after application (Klein, 2017 [29]). As a test substance chlorothalonil was used in the simulation. The simulation conditions are defined after annual applications in potatoes 14 days before harvest. A detailed description of the input parameters is available [29]. It is assumed that the HCB volatilisation of the impurity in picloram is the same.

The result of the emission factor is 1 or 100% and represents a fraction that has to be multiplied with the concentration of the applied compound.

Trend discussion for Key Sources

The following chart give an overview of the emission trend of HCB. The HCB emissions were calculated and updated for the years 2017 and 2018. HCB emissions are mainly dominated by the proportion of chlorothalonil.
According to the information of the BVL, a possible explanation for the increase of HCB emissions from 2005 onwards would be the renewed approval of Bravo 500. Possibly the first "sell-out" took place in 2014, because the approval end of "Bravo 500" was originally 30.04.2016 with a sales period until 30.10.2016 and a use-by period for users until 30.10.2017.

The end of the EU active substance approval for chlorothalonil was later extended to 31.10.2018 and again to 31.10.2019, and accordingly also the approvals for the pesticides in Germany. According to the Implementing Regulation (EU) 2019/677 [35], the BVL revoked the last three approvals for plant protection products containing chlorothalonil as of 31 October 2019. A sales deadline of April 30, 2020 applies (see https://www.bvl.bund.de/SharedDocs/Fachmeldungen/04_pflanzenschutzmittel/2019/2019_06_19_Fa_Widerruf_Chlorthalonil.html of June 19, 2019).

IIR_2020_HCB_Trend_1990-2018.PNG

Recalculations

No recalculations were made from 1990 until 2016. Only the domestic sales in 2017 were updated.

Uncertainty

For the calculation of emissions consumption figures (i. e. statistical figures) are used. Therefore, a standard error of HCB content is assumed as 2.5 % for the emission inventory. The 95% confidence interval is therefore 5 %. A normal distribution is assumed.

The uncertainty for the emission factor was determined using the PELMO model. For this purpose, the applied amounts of HCB on the plant surface were calculated with a vapour pressure reduced by a factor of 10. In addition, the meteorological conditions for modelling were selected in such a way that a range of possible emission factors for different locations was distributed across Europe (from Porto, Portugal, to Jokioinen in Finland). This results in a minimum and maximum emission factor. The maximum range was 30 %; the arithmetic mean was 10 % uncertainty (personal communication, Klein, 2017). A conservative approach and thus 30 % uncertainty is chosen for the calculation of uncertainties. This results in a total uncertainty for HCB emissions of 30.4 %.

Planned improvements

No improvements are planned for the next submissions.

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