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

Last updated on 22 Feb 2017 13:38 (cf. Authors)

Background

The list of persistent organic pollutants contained in Annex A of the Stockholm Convention on Persistent Organic Pollutants includes hexachlorobenzene (HCB). Use of HCB as a pesticide, in a pure form, has been prohibited in Germany since 1977. For this reason, no HCB emissions are reported.
However, HCB can occur as an impurity in the pesticide active substances chlorothalonil (fungicide), tefluthrin (insecticide) and pichloram (herbicide). These active substances are found in approved pesticides in Germany and continue to be used (cf. Table I, Pesticides). Tefluthrin is not emission relevant due to the application method of the insecticide.

Table I, Pesticides: Overview of pesticides (plant protection products) and their trade names, chemical agents, intended applications and approval numbers; last revision, July 2015

IIR_2017_3.d.f_tab1.PNG

HCB has never been contained in co-formulants of approved pesticides (communication of the Federal Office of Consumer Protection and Food Safety (BVL, 2015) [14].

According to the BVL, no maximum permitted HCB concentrations have ever been legally established for the technical active substances atrazine, simazine, lindane and clopyralid, nor are such limits in place today. There is also no further information available on sales of atrazine, simazine and cloparylide. Therefore the substances are not considered.

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 (2013) [10] (-3Df/3I-5, chapter 3, Tier 1 approach). It calls for calculating the maximum permitted HCB concentration from the quantities of the relevant active substance that are applied with the pertinent pesticide.

Epest = Σmpest_i • EFpest_i

Epest = total HCB emission of pesticides (in kg a-1),
mpest = mass of individual pesticide applied (kg a-1),
EFpest = EF for individual pesticide (kg kg-1).

Activity data

The outset values chosen for the activity data consist of the data published by the BVL on domestic sales of pesticides with the active substances chlorothalonil and pichloram (reports pursuant to Art. 19 (through 2011) or Art. 64 (as of 2012) of the Plant Protection Act; cf. Table II, domestic sales). The most recent data on sales of active substances consist of the data obtained by evaluating the reports through 2014.

Table II: Published data on domestic sales of active substances, in t/a, 1990 - 2014

IIR_2017_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.

The HCB quantities are calculated in light of the maximum permitted concentrations of HCB impurities established by legal acts of the EU1 or regulations of the BVL. That 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: The maximum HCB concentrations specified for chlorothalonil, a technical active substance, for 1990 and 1995, were the same for all approved pesticides (0.1 g/kg of technical active substance). The only error in the data for those years results from the assumption that the concentrations of pure active substances in the pesticides are the same as the technical active substances in them. That error is of negligible magnitude, however.

Directive 2005/53/EC, 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. Directive 2006/76/EC, which entered into force on 23 Sept. 2006, raised that standard to 40 mg/kg, which was the value then included, as of 14 June 2011, in Commission Implementing Regulation (EU) Nr. 540/2011.

For the years as of 2000, the specified maximum HCB concentrations (information provided by producers) in chlorothalonil as a technical active substance 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 this reason a transition value from the manufacturer data was determined for the year 2000 (90 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 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). That average was then 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.

Pichloram: For pichloram, a maximum concentration of 50 mg/kg has been specified for some pesticides. Relevant pesticides were introduced in Germany beginning in 2006.

Lindane: The HCB quantities in lindane were determined with the help of historically reported lindane-quantity data (cf. Table III) of the 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.

For lindane, a maximum concentration of 100 mg/kg was specified for the years 1990 through 1994. On the strength of information provided in Danish Informative Inventory Reports on persistent organic pollutants (POP-IIRs; Nielsen et al., 2014 [15]), a lower concentration, 50 mg/kg, was assumed for the years 1995 through 1997 (cf. Table IV).

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

IIR_2017_3.d.f_tab3.PNG

Table IV: Maximum concentrations of HCB impurities in relevant active substances, in g per tonne

IIR_2017_3.d.f_tab4.PNG

In recent years, the total HCB quantities in pesticide active substances (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 (0.1 g/kg), in chlorothalonil as a technical active substance, that applied prior to 2005. Due to the revised data, changes in HCB quantities occur. The maximum HCB quantity for pichloram, in the period under consideration, were lower, by factor of 20, respectively, than the relevant quantities for chlorothalonil. For this reason, fluctuations in sales of pichloram have very little impact on maximum HCB quantities. The data are extrapolated for the year 2015. An update of the data will be carried out in submission 2018.

Table V: Maximum HCB quantities in domestically sold active substances in pesticides [kg]

IIR_2017_3.d.f_tab5_1990-2015.PNG

Emission factors

Very little published information about the HCB quantities that are actually emitted during application of relevant pesticides is available that also takes account of factors such as climate, application procedures, formulations and behaviour over time (Bailey, 2001 [12]). Since HCB has a very low vapour pressure, 2.5*10-5 hPa (Fiedler, H. et al., 1995 [16]), it is assumed that the substance remains in the soil or on plant leaves after it has been applied. Because the high lipophilicity of plant cuticles in connection with polar substances presents a barrier, evaporation of pesticides from plant surfaces tends to be higher than from the soil. In the presence of water vapour, HCB is extremely volatile, even at low temperatures, as experiments carried out by Beall (1976) [13] have confirmed.
EMEP (2013) [10] )-3Df/3I-5, Table 3-1 gives an HCB evaporation factor (or emission factor) of 0.5 kg/kg. That value has been used for the emission calculation in the present context. Although it can be assumed that the volatilization rate of HCB is higher than 50 % during the application process.

Emissions

From 1990 through 2015, HCB emissions were reduced by 77 %. Restrictions and new approvals of substances with HCB lead to fluctuations in the emissions trend. Furthermore, relevant pesticides are only used when crops are at risk of infection.

Table VI: Annual HCB emissions (1990 – 2014) from pesticides in Germany, in kg

IIR_2017_3.d.f_tab6_1990-2015.PNG
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