glyphosate

Structural formula
General
Surname	glyphosate
other names	N - (phosphonomethyl) glycine
Molecular formula	C 3 H 8 NO 5 P
Brief description	colorless, odorless solid
External identifiers / databases
CAS number 1071-83-6 40465-66-5 ( ammonium salt ) 38641-94-0 (isopropylammonium salt) EC number 213-997-4 ECHA InfoCard 100.012.726 PubChem 3496 ChemSpider 3376 DrugBank DB04539 Wikidata Q407232
properties
Molar mass	169.07 g mol −1
Physical state	firmly
density	1.71 g cm −3
Melting point	230 ° C (decomposition)
pK s value	<2; 2.6; 5.6; 10.6
solubility	little in water (10.1 g l −1 at 20 ° C)
safety instructions
GHS hazard labeling from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary danger H and P phrases H: 318-411 P: 273-280-305 + 351 + 338
Toxicological data	4320 to> 5000 mg kg −1 ( LD 50 ,  rat ,  oral ) > 10000 mg kg −1 ( LD 50 ,  mouse ,  oral ) 3530 mg kg −1 ( LD 50 ,  goat ,  oral ) 1.3–25 700 mg l −1 ( LC 50 ,  fish , 96 hours ) 20–21.9 mg l −1 ( LC 50 ,  crustaceans , 48 hours ) 2.95–134 mg l −1 ( EC 50 ,  crustaceans , 48 hours ) 3.53–1080 mg l −1 ( EC 50 , algae , 96 hours )
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Glyphosate is a chemical compound from the phosphonate group . It is the main biologically active component of some broad-spectrum or total herbicides and has been marketed by Monsanto as an active ingredient for weed control under the name Roundup since the second half of the 1970s . In terms of quantity, it has been the most important ingredient in herbicides worldwide for years. Glyphosate products are sold by more than 40 manufacturers.

Glyphosate is used in agriculture, horticulture, industry and private households. It is non-selective against plants, which means that all plants treated with it die. Exceptions are crops that have been genetically modified so that they are herbicide resistant to glyphosate. The glyphosate products offered differ in the salt formulation, the medium ( solution or granulate ) and the active ingredient content . Examples of formulations are the glyphosate ammonium salt and the glyphosate isopropylammonium salt. The toxicity of ready-formulated, glyphosate-containing herbicides, such as. B. Roundup, can be higher than that of the pure active ingredient glyphosate by itself.

Compared to other herbicides, glyphosate tends to have lower mobility, shorter lifespans and lower toxicity in animals. These are usually desirable properties for agriculturally used herbicides.

An intense public and scientific debate has developed over the question of whether glyphosate can cause cancer or promote cancer production. From 2015 this discussion intensified noticeably. A European citizens' initiative called for a ban on glyphosate with almost 1.1 million valid signatures. The reason for this was the upcoming re-authorization in the EU at the end of 2017 and the assessment as “probably carcinogenic” for humans by the International Agency for Research on Cancer (IARC).

Other authorities and organizations contradicted this assessment, including the European Food Safety Authority (EFSA), which took over the assessment of the Federal Institute for Risk Assessment (BfR). A Joint Meeting on Pesticide Residues (JMPR) of the World Health Organization (WHO), USEPA , Health Canada and the European Chemicals Agency (ECHA) also came to the conclusion that glyphosate in food is not carcinogenic. These differences in the results are also attributed to different approaches to the assessment. According to research by the television magazine Monitor , studies by the agricultural economist Michael Schmitz on the benefits of glyphosate were partially funded by Monsanto.

history

The Swiss chemist Henri Martin , who was employed by Cilag , synthesized glyphosate for the first time in 1950. The new compound was neither described in the literature nor marketed. 1959 Cilag was taken over by Johnson & Johnson and glyphosate was sold to Sigma-Aldrich along with other samples . Sigma-Aldrich also only sold small amounts of the substance in the 1960s, the biological activity of which was still unknown. Monsanto was testing several water softening compounds at the time , including a. about 100 variants of aminomethylphosphonic acid . In tests conducted by the chemist Phil Hamm on the herbicidal effect of these variants, two compounds with an - albeit low - effect were found. John E. Franz , another scientist working for Monsanto, analyzed the metabolic effects of these two compounds in plants and, based on this, developed derivatives of these substances, including glyphosate as one of the possibly more herbicidal products. Monsanto first synthesized the compound in May 1970 and patented glyphosate as a herbicide in 1971. The patent was granted in 1974.

The substance came onto the market for the first time in 1974 as an active ingredient in the herbicide Roundup , which also consists of other substances . Initially, the inexpensive glyphosate was used as an active ingredient in agriculture to clear the fields of weeds before they were re-sown. In the 1990s, genetically modified plants with glyphosate resistance were approved. This made it possible to use herbicides containing glyphosate even after sowing and during the entire subsequent growth of the plants.

production

Glyphosate was manufactured by at least 91 chemical companies in 20 countries in 2015. In China alone there are 53 manufacturers, in India 9 and in the USA 5. The amount produced was estimated at 600,000 tons of glyphosate in 2008, 650,000 tons in 2011 and 720,000 tons in 2012. More than 40% of the glyphosate is made in China. In 2016, Chinese companies exported over 70,000 tons of glyphosate and formulations.

The patents on the production of glyphosate expired in 2000.

Extraction and presentation

Glyphosate can be obtained by reacting phosphorus trichloride with formaldehyde and water and then reacting the chloromethylphosphonic acid, which is formed as an intermediate, with glycine . It is also possible to display it by reacting diethyl phosphite (or phosphonic acid ) with formaldehyde, glycine (or ethyl glycinate ) and hydrogen chloride . A similar synthetic route shown below to the reaction scheme in which instead of di -ethyl phosphite, di methyl is assumed phosphite and not drawn hydrochloric acid causes the final Esterspaltung on the phosphorus atom:

The representation of glyphosate shown in the reaction scheme is used in the majority of industrial glyphosate production in China.

properties

Glyphosate ions and pK _S values

Glyphosate is an odorless, water-soluble and non- volatile substance. Glyphosate is produced as an acid and a salt.

Glyphosate is an amphoteric compound, and therefore has several pK _S values . Because of its high polarity , the substance is practically insoluble in organic solvents.

Industrially produced glyphosate has an average purity of 96% dry weight . The rest is distributed among some by-products of the synthesis. The proportion of by-products is less than one percent each.

A typical glyphosate formulation contains 356 g / l glyphosate or 480 g / l isopropylamine glyphosate plus a wetting agent to improve penetration into the plant.

Analytics

Due to their high polarity , glyphosate and its most important metabolite AMPA are difficult to separate using liquid chromatography . This is why it is implemented with Fmoc during processing according to ISO 21458 . The resulting derivatives can then be detected using a fluorescence detector . Modern methods provide for liquid chromatography with tandem mass spectrometry (LC-MS / MS). The coupling of gas chromatography with mass spectrometry is also suitable for the analysis of breast milk and urine samples. More recent studies have also been able to reliably detect glyphosate in honey samples.

Mechanism of action

Shikimate                                                         Shikimate-3-phosphate       glyphosate                           v PEP → === ← EPSPS                                             5 ‑ enolpyruvyl shikimate ‑ 3 ‑ phosphate                                                         Chorismate                                                                       Prephenate       Anthranilate                                                           Phenylalanine   Tyrosine   Tryptophan

How glyphosate works

Glyphosate blocks the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS), which is required for the synthesis of the aromatic amino acids phenylalanine , tryptophan and tyrosine via the shikimate pathway in plants, as in most microorganisms. The reason for the blockage is the chemical similarity of glyphosate to phosphoenolpyruvate (PEP), the regular substrate of EPSPS. Glyphosate is the only known herbicidal agent that effectively blocks EPSPS.

Environmental behavior

Because of its chemical similarity to the phosphate ion, glyphosate is attached (“ adsorbed ”) to the same soil minerals to a similar extent as phosphate itself. Both adsorb strongly on aluminum and iron oxides, for example. A high phosphate concentration in the soil could hinder the adsorption of glyphosate through competition and thus lead to a higher leaching of glyphosate from the rooted soil zone. However, various laboratory and field studies have found no or only a limited influence of phosphate for most minerals and soils.

Because of its strong adsorption in the soil, glyphosate is only rarely detectable in groundwater samples and mostly in low concentrations. The proportion of active ingredient rinsed out by surface runoff from an area treated with glyphosate is usually less than one percent of the amount applied. Across Europe, the proportion of measuring points at which the prescribed limit value of 0.1 µg / l in the groundwater was exceeded was less than 1%. Values ​​above the limit value were possibly a. found in Italy, Germany, the Netherlands, Denmark, Norway, France and Spain. On the basis of the data collected by the Länderarbeitsgemeinschaft Wasser (LAWA) for Germany, glyphosate was measured in 0.4 to 0.5% of the samples in concentrations higher than the prescribed limit in the groundwater in 2008, 2009 and 2011.

In the Argentine Pampa of the samples (n = 112) in the glyphosate were 2012 to 2014. in 81% rainwater (0.50 to 67.3 g / l) were detected ( detection limit 1 ug / l). Values ​​between 28 and 323 μg / kg were measured in 41% of the soil samples examined (n = 58) (limit of quantification 5 μg / kg).

This article or section needs to be revised: The limit of quantification , which allows better classification of the results, is missing.
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In some countries, glyphosate is used against aquatic plants that float on or protrude from the surface. After such actions, glyphosate concentrations of 0.010 to 1.700 mg ae / l (ae = acid equivalent ) were measured in the water ; in the sediment the concentrations were between 0.11 and 19 mg ae / kg dry weight.

In sterile water, glyphosate is stable over a wide range of pH values; a hydrolysis hardly takes place. Even with additional exposure to sunlight ( photolysis ), glyphosate was degraded to less than 1% in the pH range of 5–9 after 30 days. Photolysis degradation rates are very low when glyphosate is in or on soil surfaces. In rivers, in addition to microbial degradation, adsorption on sediments and suspended particles as well as dilution by further inflows ensure a decrease in the glyphosate concentration in the water. The rate of degradation in standing water depends on local conditions. The half-life for the degradation of glyphosate in water bodies is estimated to be 7 to 14 days.

Glyphosate degradation pathways in the soil

Glyphosate is mainly broken down by microorganisms in the soil - both under aerobic and anaerobic conditions. The rate of degradation depends primarily on the microbial activity of the soil. The breakdown takes place mainly via AMPA (aminomethylphosphonic acid) or via glyoxylic acid and ends with the release of carbon dioxide , phosphate and ammonium. According to field studies on arable land, the half-life for glyphosate in the soil ( DT ₅₀ value ) is on average 14 days and around 30–60 days in forest ecosystems. In 47 field tests on arable and forest areas in Europe and North America, the DT _{50 was} between 1.2 and 197 days, the average from all studies was 32 days.

Due to the low volatility of glyphosate, the evaporation of the applied active ingredient from the field is negligible. The drift onto neighboring surfaces depends on the weather and the spray equipment used. With modern field sprayers, about 4% of the rate of application of pesticides still reaches a distance of 1 meter from the edge of the field due to drift. When using agricultural aircraft , the drift is greater; at a distance of 25 meters it is still 10% of the application rate, and at a distance of 75 meters it is 1%.

Formulations and co-formulants

In its pure (protonated) form, glyphosate is a crystalline solid which, when dissolved in an aqueous solvent with a pH of 2, reacts strongly acidic. The solubility is low (about 1%, at 25 ° C). In commercial applications, glyphosate is therefore used in the form of a salt; common cations are, depending on the product, isopropylamine , ammonium or potassium . In this form, the solubility in water increases to almost 50 percent. The salt form is important when studying environmental impact and toxicity. For example, a study in Japan showed that "massive" intake of the potassium salt of glyphosate can trigger life-threatening hyperkalaemia due to its potassium content .

The glyphosate salt in the finished herbicide is usually not applied in its pure form. In addition to the active ingredient glyphosate, they contain various co-formulants (including formulation auxiliaries or adjuvants ) that are intended to change the properties of the product in a way that is favorable for the application. In particular, as a very polar substance , glyphosate is only slightly effective in its pure form, as it rolls off the hydrophobic cuticle of most plants. Effective co-formulants are therefore added as surfactants ( English surfactants ). The composition of a plant protection product from active ingredients and co-formulants is called “formulation”. So many glyphosate-containing herbicides include the polyethoxylated tallow amine POE-15 as a surfactant which 10,000 times stronger in laboratory tests mitochondria damaged than glyphosate itself: the toxicity of the inert components may be much higher than that of the active ingredient. It is essential to bear this in mind with published results, as these are partly based on tests of the pure active ingredient and partly on those on finished products, which can result in very different results. For example, it is now considered likely that the high toxicity of the glyphosate-containing herbicide Roundup on amphibians is more due to the added sebum amine oxyethylate than to the active ingredient itself.

Application and meaning

Glyphosate is a non-selective leaf herbicide ( broad spectrum or total herbicide ) with systemic effects that is absorbed through all green parts of the plant. Glyphosate is used in agriculture against monocotyledonous and dicotyledonous weeds in arable, wine and fruit growing, in the cultivation of ornamental plants, on meadows, pastures and lawns as well as in the forest. The leaves take up glyphosate by diffusion . Most glyphosate formulations contain surface-active substances (so-called wetting agents or spreaders), which ensure that the leaves are evenly wetted and thus improve absorption. In the plant, glyphosate is distributed via the phloem . Glyphosate that reaches the soil is adsorbed there and can therefore only be absorbed by plants to a small extent. Sowing or replanting can be done soon after the herbicide has been applied.

Use of glyphosate to keep the tree slice free on an apple orchard

Since glyphosate over all green parts of plants such. B. the leaves are picked up, it is used in crop production before the actual crop is sown. At this point, however, many of the weeds have often already emerged; H. they have green plant parts that can be hit by the glyphosate application. Spraying shortly after sowing is also common. Weeds that germinate quickly and superficially are hit by this, while the crops sown deeper later germinate ('emerge') and are spared (see: pre-emergence or pre-emergence herbicide ).

Glyphosate can be used in vineyards and orchards if there are no leaves from the vines or fruit trees in the application area close to the ground (see figure on the right).

Crops that are resistant to glyphosate (due to genetic engineering methods ) are already being grown in many countries. For genetically modified, glyphosate-resistant crops such as soybeans, rape, cotton and maize, glyphosate can also be used after the plants have already sprouted. It can be used not only before sowing - as with conventional plants - but at different times of cultivation. The necessary mechanical tillage is thereby reduced. The assertion that the cultivation of resistant crops increases the use of herbicides is not true, although resistant plants tolerate the treatment better. The combination of glyphosate-resistant field crops + multiple glyphosate applications and the high degree of application in several large growing countries is justified by the economic advantages of this form of weed control. Incidentally, in Europe too, a field is generally kept as weed-free as possible, mostly with herbicides. In addition to glyphosate-resistant crops, herbicide- resistant weeds , especially those with glyphosate resistance, have also developed, such as Amaranthus palmeri , which can no longer be combated through the use of glyphosate alone.

Europe

European Union

A study published in 2014 examined the consequences of a possible ban on glyphosate for seedbed treatment in winter cereals and rape in the EU-25 . If glyphosate were eliminated, farmers would increasingly switch to mechanical treatment and selective herbicides for their weed control. Without significant adjustments and innovations in cultivation, they would suffer high yield losses, which could add up to 14.5 million tonnes in the EU-25. In order to maintain the previous level of production despite lower yields, the cultivation area would have to be expanded by up to 2.4 million hectares. Such an expansion would lead to increasing greenhouse gas emissions. Alternatively, more agricultural products could be imported from outside the EU.

Germany

In Germany around 37 percent of arable land is treated with glyphosate every year (as of 2017). The amount of active ingredient applied is estimated at around 5000 tons. In 2014, 5330 tonnes of glyphosate were applied to German fields, in 2012 it was 5941 tonnes. In the private sector, i.e. by house and allotment garden users, a total of 95 tonnes were used in 2014, compared to only 40 tonnes in 2012.

Glyphosate is used in German agriculture at three different times:

• Stubble applications, including post-harvest applications (around 60%, corresponds to 22% of the total arable area). The herbicide is applied after the harvest in order to control weeds or preculture crops that have grown from failed seeds (e.g. rape), known as volunteers . This also serves the so-called. Field hygiene to z. B. to offer pests no reservoir.
• Pre-sowing applications (about 34%, corresponds to 13% of the total arable area). Herbicide is applied shortly before or a few days after sowing (before the crop has germinated). This is important for conservation tillage, to reduce soil erosion, especially plowless tillage and mulch sowing . Another field of application is the control of weeds that have developed resistance to numerous other herbicides, such as the wind stalk and foxtail .
• Pre-harvest applications (around 6%, corresponds to 2% of the total arable land). Here, the total herbicide kills the crop itself together with any weeds that may be present. This is done in the context of a so-called siccation in the event of uneven emergence of the crop, winter damage, damage from heavy rain, hail or storms to enable a uniform harvest time and to combat late weed growth and weed growth in combine crops. The use of glyphosate to facilitate harvesting is only permitted in crops in which harvesting would otherwise not be possible. In cereals, weed control is only permitted for stocks that are in storage. In Germany, pre-harvest treatment has only been permitted for particularly difficult harvest situations since 2014, but no longer for controlling the harvest date ( threshing ). Siccation is prohibited in Switzerland.

Steinmann et al. (2012) put the benefits of glyphosate in Germany at EUR 79–202 million per year. They assume that there would be no loss of yield without glyphosate, since an increased use of plows and other herbicides for weed control would compensate for such effects.

In 2015, the Julius Kühn Institute (JKI) published an impact assessment for the partial or complete abandonment of glyphosate-containing herbicides in German agriculture. According to the JKI, the complete replacement of glyphosate by (the more expensive) mechanical weed control in permanent crops (especially apples) would have serious consequences and would hardly be economically justifiable. In arable farming, under favorable conditions (depending on location, weather and cultivation practice), mechanical weed control can lead to an economically identical or even better result. Under unfavorable conditions, the replacement of glyphosate by mechanical processes leads to yield losses; in the case of bread wheat, these losses correspond to 6 to 17% of the contribution margin. In order to achieve a cost equivalence of three tillage operations with the glyphosate application, the glyphosate prices would have to increase by approx. 75%. However, other factors are also decisive for the economic advantage, such as sufficient field working days and labor capacities as well as sufficient mechanization. Also, no drying should be necessary after the harvest. The JKI recommends that glyphosate use should not be viewed from the outset as a standard measure in arable farming and that mechanical operations should be considered as a flexible alternative in certain situations (e.g. alternating with glyphosate every year).

According to its own information, Deutsche Bahn AG uses around 60 to 70 tons of glyphosate and other herbicides every year to keep the tracks free of growth. The Deutsche Bahn is currently looking for alternatives, whereby the necessity of compatibility of these alternatives for the protected sand lizard living on railway embankments makes the search more difficult and the additional costs compared to the use of glyphosate are estimated at a factor of 10. As of 2020, the railway will no longer apply glyphosate and is testing alternatives to what extent weeds can be removed with hot water, electricity or UV light. Superheated steam, microwaves and high-frequency energy have already been rated as very time-consuming and energy-consuming.

In 2015, Hessen banned the use of glyphosate on municipal land. A hot water system with a comparable effect is already being used in the Felsberg municipality . According to Mr. Semmler, an employee of the municipality, the hot water is even superior to glyphosate in some respects. He cites the advantages: “Hot water can also be sprayed near sewers, glyphosate cannot. Hot water can be applied up to eight times a year, glyphosate only twice. "

Austria

According to the Austrian Federal Office for Food Safety, around 312 tons of glyphosate were sold in 2016. Thus the amount sold is slightly lower than in the previous year at 327 tons.

In March 2019, the federal state of Carinthia , where glyphosate has not been used by public authorities for several years, completely banned its use, including for private users, after a request to the EU Commission was positive.

On July 2, 2019, Austria became the first country in the European Union to ban the use of glyphosate. The National Council approved a majority of an SPÖ motion. The ÖVP spoke out against the ban. However, it is controversial whether the ban is compatible with EU law. Nevertheless, the environmental protection organization Greenpeace spoke of a "historic milestone".

After the EU did not have a veto until December 2019, the law could have come into force as planned at the beginning of 2020. The EU had previously noted that the draft and not the adopted law should have been notified, which means that the Ministry of Agriculture sees the risk of legal uncertainty and the associated lawsuits. Because of this formal error, it was decided not to put the ban into force for the time being.

Switzerland

In Switzerland, 204 tonnes of the active ingredient were sold in 2016, compared to 296 tonnes in 2014. The Swiss Federal Railways use 2.5 to 4 tons of glyphosate annually for weed control on the track beds .

United Kingdom

According to a study published in 2010 (Cook et al. , 2010), a glyphosate ban would have significant consequences for agriculture and the environment. Without glyphosate, farmers would plow more often, which would increase the workload by 50%. More machines would also be necessary, harvested grain would also have to be dried and its quality would decrease. The authors estimated additional costs of £ 473 per hectare for wheat and £ 470 per hectare for rapeseed. In addition, food prices would rise. With regard to the environment, the elimination of tillage without a plow would lead to increased soil erosion, waterlogging and the loss of organic matter and biodiversity. Loss of productivity would lead to an expansion of the cultivation area and increased imports of wheat and rapeseed. More frequent plowing and the conversion of grass to arable land to compensate for lower yields would increase greenhouse gas emissions by an estimated 12 million tonnes of CO ₂ equivalent .

United States

Estimated application volume in the USA from 2013 to 2013

In 2007, no herbicide was used in US agriculture more than glyphosate-containing products. A total of more than 110,000 tonnes were used in 2011, the majority of which was used in soy and corn cultivation. In addition to Roundup , dozens of other glyphosate-containing herbicides are on the market, for example Clinic from Nufarm , Glyfos from Cheminova , Touchdown from Syngenta or VOROX Weed-Free Direct ( Compo ).

Effect on non-target organisms

The effects of glyphosate on non-target organisms have been extensively studied, including by the USEPA , the WHO and the EU . Almost all individual scientific studies, reviews and authorities confirm that the approved uses of glyphosate do not pose any health risks. Non-governmental organizations such as Naturschutzbund Deutschland , Greenpeace or Friends of the Earth , citing isolated studies, take the position that glyphosate poses considerable health and environmental risks.

The toxicity of glyphosate for animals (mammals, birds, fish and invertebrates) is low, since the inhibited enzyme EPSPS is only present in plants, fungi and microorganisms. The toxicity of glyphosate-based products can be influenced by their formulation . For example, the use of wetting agents (as in Roundup ) leads to higher toxicity, especially in aquatic animals. As the isopropylammonium salt, glyphosate is less toxic, especially to fish. Ingested glyphosate is excreted quickly and unmetabolized by animals.

Absorption into the body

In rat feeding studies, orally administered radioactively labeled glyphosate was absorbed into the body at a rate between 15 and 36%, the rest was excreted in the faeces. The highest percentage intake rates were achieved at low dosages. Ingested glyphosate was for the most part excreted unmetabolized. About 10% of the administered glyphosate was detectable in the urine , less than 0.3% appeared as CO ₂ in the exhaled air, and most of it was released with the faeces. Feeding studies on rabbits, dairy goats and chickens showed a comparable intake rate and corresponding glyphosate levels in tissues as well as in milk and eggs.

Both from undiluted Roundup solution and from a spray solution, skin samples absorbed up to 2% of the glyphosate contained in the solution over an exposure time of 16 hours. According to a study, the absorption of glyphosate through the skin of exposed persons does not result in a potential risk of damage to health.

The detailed studies in the exposure of farmers observed maximum systemic exposure is 0.004 mg / kg. The maximum value without toxic effects (NOEL) is 175 mg / kg / day.

The European Food Safety Authority assumes that food residues of 0.3 mg / kg for maize and 7 or 10 mg / kg for soybeans do not pose a long-term health risk for the consumer. However, the limit values ​​are now 1 mg / kg for maize and 20 mg / kg for soybeans.

The joint meeting (2004) of the Food and Agriculture Organization and the World Health Organization on the risk assessment of pesticide residues in 32 foods came to the conclusion that glyphosate residues are not associated with any acute or chronic health risks for the consumer.

Exposure of pregnant women

A systematic review published in 2016 examined whether glyphosate exposure during pregnancy could have adverse effects such as an increased risk of malformations , premature births or miscarriages . Except for a possible association with ADHD , no negative effects were found.

In the context of a study from Thailand published in 2017, it was found that women who work in agriculture or whose family members work in agriculture and who were 7 months pregnant between May and December 2011 had elevated levels of both paraquat and glyphosate at birth in their own blood serum as well as in the blood serum of the umbilical cord. The authors conclude that research should be carried out on the long-term effects of prenatal exposure to glyphosate on children's health, and that more stringent regulation of pesticide use and sales could protect children's health in Thailand.

In a study published in 2018 on glyphosate exposure in pregnant women between 2015 and 2016 in the United States, scientists found that more than 90% of women had detectable glyphosate levels and that these levels correlated significantly with shorter gestation periods . Although the cohort study was small, regional and showed limited ethnic diversity, it provides direct evidence of maternal glyphosate exposure and a significant correlation with a shortened pregnancy. Further research in a more geographically and ethnically diverse cohort would be needed before these results could be generalized.

Glyphosate in breast milk

In a random test ( n = 16) on behalf of the party Die Grünen , residues of glyphosate were found in all 16 breast milk samples. On June 30, 2015, the BfR and the National Breastfeeding Commission stated that the measured levels of up to 0.43 nanograms (ng) per milliliter (ml) (corresponds to 0.43 μg / liter) are harmless to health. The published values ​​would lead to a glyphosate intake in newborns that is a factor of more than 4000 lower than the guideline value derived in the EU, at which no health risks are to be expected. In addition, according to the BfR, there are considerable doubts about the methodology of the test.

The BfR then commissioned a study in which two independent analytical methods with high sensitivity were developed and 114 breast milk samples from Lower Saxony and Bavaria were examined. The study found no glyphosate residues. According to the BfR, due to the physico-chemical properties of glyphosate, no relevant transfer of the active ingredient into breast milk is to be expected and has not yet been scientifically proven. The study was published in January 2016 in the Journal of Agricultural and Food Chemistry .

In April 2014, the anti-genetic engineering organization Moms Across America (MAA) published the results of analyzes that reportedly found glyphosate residues in breast milk in three out of ten samples. The analyzes were carried out by a contract research company on behalf of MAA and Sustainable Pulse with the support of Environmental Arts & Research. A study first published in July 2015 (published in The American Journal of Clinical Nutrition in March 2016 ) by Washington State University found no glyphosate in breast milk in agricultural regions of Washington where glyphosate is routinely used. The milk samples were examined by Monsanto laboratories in St. Louis and the analysis results were independently verified at a contract research institute located in Wisconsin.

Bus (2015) came to the conclusion in a study funded by the Glyphosate Task Force that the non-peer-reviewed results of the MAA were not plausible, i.e. H. are implausible.

Glyphosate in the urine

See also: "Urinals 2015" campaign

In spring 2013, 182 urine samples from 18 European countries were tested for glyphosate and its degradation product AMPA ; the study was financed by the Association for the Environment and Nature Conservation Germany and Friends of the Earth . The mean values ​​of the determined concentrations were 0.21 µg / l for glyphosate and 0.18 µg / l for AMPA, with a limit of quantification of 0.15 µg / l in each case. The maximum values ​​found were 1.56 µg glyphosate and 2.63 µg AMPA per liter. Although glyphosate was detected in 44% of the samples examined, the measured concentration in the urine, according to the statement of the Federal Institute for Risk Assessment (BfR), is “far below a range that is hazardous to health” (factor 1000). In humans, 20-30% of the glyphosate from food is absorbed through the intestines and then mostly excreted in the urine .

A review article published by BfR scientists in the Journal for Consumer Protection and Food Safety in 2015 analyzed seven studies from the USA and Europe in which glyphosate was found in urine. The work comes to the conclusion that no health hazards were identified, as the exposure levels were several orders of magnitude below the ADI and AOEL values.

After Monsanto introduced genetically modified crops that are resistant to glyphosate so that key crops such as corn, soybeans and cotton could be sprayed with the herbicide, the use of glyphosate in the United States and , according to a report by Pulitzer Prize winner Danny Hakim other parts of the world have increased sharply over the past two decades. During that time, the prevalence of detectable glyphosate in human urine increased five-fold, according to a study by the University of California's San Diego School of Medicine . For the prospective study , data from 100 subjects over the age of 50 from Southern California from 1993 to 2016 were compared. Since studies suggest that chronic exposure to formulations containing glyphosate can cause health problems in animals and humans, the study authors see a need for further research here. They refer to von Robin Mesnage et al. Conceived feeding experiments in which test animals exhibited changes in liver metabolism under constant very low glyphosate concentrations, which were comparable to the effects of non-alcoholic fatty liver and its further development into steatohepatitis .

toxicity

According to the guidelines on drinking water quality of the World Health Organization (fourth edition, 2011), the residue levels of glyphosate in drinking water are far below levels that are harmful to health.

The European ADI is 0.5 mg / kg. The AOEL is 0.1 mg / kg body weight.

The half-maximal inhibitory concentration (IC ₅₀ ) of progesterone in mouse cell cultures is according to a study at 24.4 mg / l for Roundup.

Controversy over Richard et al. (2005)

The journal Environmental Health Perspectives published a study in 2005 (Richard et al. , 2005) from the group of Gilles-Éric Séralini . According to this, Roundup is for the cells of a cell line (JEG3), which comes from a tumor in a human placenta , in vitro and in high concentrations (up to 2% solution of Roundup in water, corresponds to up to 7.2 g / l glyphosate) Toxic within 18 hours. In addition, the activity of aromatase is reduced and the study concludes that Roundup is an endocrine disruptor . Furthermore, it was found that glyphosate itself does not explain the toxicity and, after adding only 0.1% Roundup solution to a solution containing only glyphosate, drastically reduces cell viability . Roundup varies in composition and, in addition to the active ingredient glyphosate, usually also contains the wetting agent tallow fatty amine oxethylate , which has been proven to damage placental cells. However, the study did not mention which Roundup formulation was used and which other substances besides glyphosate were included.

Monsanto criticizes the methodology of the study. The exposure scenario is unrealistic and has no relevance for living animals. The concentrations used are far higher than the highest concentrations that can be achieved under realistic conditions. The study does not take into account the low intake and metabolism to which glyphosate is subject and which protects the organism from such high concentrations. Furthermore, the cell line would be used in research, but would not be recognized by any scientific institute or regulatory agency for the determination of health risks. Monsanto also says they reproduced the study with Roundup, but also with household chemicals, and found that the endocrine disruption was due to damage to the mitochondrial membrane rather than a glyphosate-specific mechanism.

The BfR also commented on the study. According to the French Commission for Toxicology (Commission d'Etude de la Toxicité), the study had methodological flaws and incorrect arguments and interpretations and was useless for a risk assessment.

Controversy over Benachour & Seralini (2009)

In 2009, the journal Chemical Research in Toxicology published a study (Benachour & Seralini, 2009) by Gilles-Éric Séralini's group on experiments with various glyphosate-containing pesticides and human cells. Cell death was induced in sufficient concentration, and the authors concluded possible health risks for humans from this.

The then French Food Safety Agency (AFSSA) criticized the study for several reasons, stating that the study could not question the existing assessment of glyphosate at EU level or the assessments of plant protection products containing glyphosate at national level.

Carcinogenicity and Genotoxicity

For a long time, glyphosate was rated relatively unanimously as not carcinogenic. According to a review published in 2000 (Williams et al. , 2000), extensive studies in experimental animals have shown that there is no evidence of carcinogenicity , mutagenicity , neurotoxicity or reproductive toxicity for humans.

In an evaluation from the year 2000, the USEPA placed glyphosate in a group of substances for which there is evidence that it is not carcinogenic to humans.

A 2012 review, supported by Monsanto , examined 21 epidemiological studies (seven cohort studies and 14 case-control studies ). The review failed to find a consistent pattern of positive association suggesting a causal relationship between cancer (and individual cancers) and glyphosate exposure.

A review article (Kier and Kirkland, 2013) supported by the Glyphosate Task Force (an association of various plant protection product companies led by Monsanto that have submitted a joint application for the re-authorization of the herbicidal active ingredient glyphosate in the European Union) carried out genotoxicity and authorization studies on glyphosate and glyphosate-containing crop protection products that have been used since Williams et al. (2000) published together. The results were analyzed using a weight-of-evidence method for genotoxicity. According to the work, glyphosate and common glyphosate-containing plant protection products do not pose a significant genotoxic risk under normal exposure conditions. In 2015, a Monsanto-supported review by Kier was published, which summarized existing biomonitoring studies and confirmed the results of Kier and Kirkland (2013).

In March 2015, the International Agency for Research on Cancer (IARC) of the World Health Organization (WHO) classified glyphosate in category 2A (probably carcinogenic for humans, probably carcinogenic to humans ), see also IARC assessment . One of the external reviewers was the statistician Christopher J. Portier.

Another review, supported by the Glyphosate Task Force and published in 2015, examined 14 carcinogenicity studies that were used in regulatory processes. The review comes to the conclusion that there is no evidence of carcinogenic effects in connection with glyphosate applications. There was a lack of a plausible mechanism and epidemiological studies that showed a clear, statistically significant , unbiased association between glyphosate and cancer. The weight-of-evidence method demonstrates that glyphosate has no carcinogenic potential in humans.

In June 2015, USEPA tested glyphosate as part of its Endocrine Disruptor Screening Program . Based on the scientific knowledge based on the weight-of-evidence method, it determined that there was no convincing evidence for potential interactions of glyphosate with estrogen, androgen and thyroxine. Based on the result, the USEPA sees no need to carry out any further tests.

On November 12, 2015, the EFSA and EU member states' re-evaluation of glyphosate was published. According to the conclusions of the report, glyphosate is unlikely to pose a carcinogenic hazard to humans.

The Joint FAO / WHO Expert Committee on Pesticide Residues (JMPR) has assessed glyphosate for carcinogenicity several times since 1993, most recently in 2016. According to the assessments, the residues of glyphosate ingested in humans are probably non-genotoxic and non-carcinogenic.

The Japanese Food Safety Authority (FSC) found no evidence of carcinogenicity or genotoxicity in a comprehensive risk assessment of glyphosate published in 2016.

A systematic review and meta-analysis published in 2016, sponsored by Monsanto , investigated the association between glyphosate exposure and the lymphohematopoietic cancers non-Hodgkin lymphoma (NHL), Hodgkin lymphoma (HL), multiple myeloma (MM) and leukemia . There were marginally significant, positive meta- relative risks (RR) for an association of glyphosate use with NHL and MM and no association with HL and leukemia. In the opinion of the authors, however, there are methodological problems with the small number of studies and, overall, the literature is weak, inconsistent, ambiguous and does not show any positive biological gradients , which is why a causal relationship between glyphosate exposure and the types of cancer studied cannot be concluded.

In September 2016, the USEPA published its assessment of the carcinogenic potential of glyphosate as part of the routine (at least every 15 years) approval review. The assessment was made on the basis of all available studies and is “probably not carcinogenic”.

As part of the approval procedure, a classification proposal was submitted to ECHA , which could be commented on between the beginning of June and July 18, 2016. On March 15, 2017, the ECHA Committee for Risk Assessment (RAC) classified glyphosate as Eye Damage 1 , H318 and Aquatic Chronic 2 , H441. According to the RAC, the available scientific knowledge does not meet the criteria of the CLP Regulation for classification as specifically organ- toxic , carcinogenic , mutagenic or toxic to reproduction . The ECHA classifications are based on the hazard analysis ( "Hazard Assessment") and tighten exposure and risk out of the question. When asked why ECHA came to a different conclusion than the IARC, the agency replied that different researchers could “interpret and weight differently” scientific findings. In addition, approval authorities would also evaluate studies by industry that are not publicly available. The IARC, on the other hand, refuses to use industry data that is not available to the public at the time of evaluation.

In April 2017, Health Canada published a reassessment of glyphosate that glyphosate is non-genotoxic and unlikely to be carcinogenic to humans.

A comprehensive prospective cohort study of almost 45,000 glyphosate users published in November 2017 came to the conclusion that there was no statistically significant association between glyphosate and the occurrence of solid tumors or malignant lymphomas. However, the study indicates that users of high doses of glyphosate tend to have an increased risk of acute myeloid leukemia (AML) . This tendency of the finding is corroborated in a meta-analysis that focuses on a group of people who use high doses of glyphosate. This epidemiological study shows a 40% statistically significant increase in the risk of developing non-Hodgkin lymphoma (NHL), which also includes AML. The authors point out that animal experiments and studies of the mechanism of action would support this finding.

Assessment of the IARC (2015)

The International Agency for Research on Cancer (IARC) concluded in March 2015 that there was limited evidence of the carcinogenic potential of glyphosate in humans. The evidence that the substance leads to tumors in rats and mice was considered sufficient. The IARC therefore classified glyphosate in category 2A (probably carcinogenic for humans, probably carcinogenic to humans ).

On July 29, 2015, the detailed justification of the IARC regarding the assessment of glyphosate was available online. The IARC based its assessment of carcinogenic effects in humans mainly on several case-control studies and the Agricultural Health Study (AHS), an epidemiological cohort study of 57,311 farmers from Iowa and North Carolina . Case-control studies from the United States, Canada, and Sweden showed an increased risk of developing non-Hodgkin lymphoma (NHL), while AHS showed no association between glyphosate exposure and NHL. Three studies indicated a possible connection between glyphosate and multiple myeloma , but the IARC believes that there is greater uncertainty here. According to the IARC, there was no evidence of glyphosate-favored cancers of the brain, esophagus, stomach or prostate or soft tissue sarcomas in the few studies carried out . In a feeding study in mice cited in the IARC assessment, there was a significant increase in adenomas or carcinomas of the renal tubules in males , but not in females. In another study in mice, the incidence of hemangiosarcomas increased in males , but not in females. Of the evaluated feeding studies on rats, two showed a significant increase in islet cell adenomas of the pancreas in male rats , one of them also for liver cancer (hepatocellular adenoma) in males and for thyroid adenomas (thyroid C-cell adenoma) in females. Two other studies cited by the IARC did not show a significant increase in the rate of one type of cancer. A glyphosate-containing formulation had the mice promotion of skin tumors result. The IARC regards the genotoxic effects of glyphosate as well documented. The fact that glyphosate, its breakdown product AMPA and glyphosate-containing formulations trigger oxidative stress has also been well documented.

Responses to IARC Assessment

The Joint FAO / WHO Expert Committee on Pesticide Residues (JMPR) clarified the different and complementary roles of IARC and JMPR within WHO: IARC identifies and classifies hazards, while the JMPR assesses the risks of pesticide residues. The JMPR recommended a reassessment of glyphosate because the last evaluation was more than ten years ago and new studies have appeared in the meantime. The World Health Organization did not change the recommendations for use of glyphosate and advised against political or regulatory reactions, including bans, until the JMPR has completed the reassessment. (The JMPR reassessment was published in May 2016.)

The German Federal Institute for Risk Assessment (BfR) announced in a background information in September 2015 that it had examined and assessed all available studies in a scientifically sound manner, including those cited by the IARC. According to the BfR, both the BfR and the assessment authorities of the EU and other countries as well as the IARC have come to the conclusion that these studies have only provided limited indications of the carcinogenicity of glyphosate-containing plant protection products (mixtures of active ingredients and co-formulants). These studies are of little relevance for the evaluation of the pure active ingredient glyphosate (with which the BfR is commissioned). The BfR expressly recommends checking the formulations of plant protection products containing glyphosate as part of the national approval process. In December 2015, the BfR stated that the IARC was carrying out a purely hazard-related analysis, which, however, did not take into account the likelihood that cancer would actually be produced because this was dependent on the amount of intake. In contrast, the BfR undertakes a risk-related assessment in the approval process for active pesticide substances. In addition to the hazard-related analysis of a substance, this also takes into account the estimated exposure, i.e. the actual intake of the substance, and uses this information to determine the risk of developing cancer.

In response to the IARC assessment, Health Canada noted that identifying a hazard is not a risk assessment . The exposure , which ultimately determines a risk, was not taken into account by the IARC. The Australian pesticide and veterinary medicine authority APVMA also pointed out that the IARC assessment is a pure hazard assessment and does not include the type of use (exposure).

The Swiss Federal Office for Agriculture reacted with reluctance to the IARC assessment and announced that it would examine the studies on which the IARC assessment is based.

According to EFSA (November 2015), the IARC assessment not only assessed the active ingredient glyphosate, but also took into account studies with glyphosate-based formulations that contain other substances in addition to glyphosate and in different doses. This is important because some studies have indicated that certain glyphosate-based formulations may be genotoxic, while others, which only look at the active ingredient glyphosate, did not show this effect. This could explain the differing assessment of the IARC. EFSA also stated that it had considered a larger number of studies than IARC and that, for example, some carcinogenic effects observed at high doses were not conclusive because they could be due to general toxicity.

According to an assessment by ANSES published in February 2016, glyphosate cannot be classified in the first category (known or likely to be carcinogenic in humans) according to the CLP Regulation due to a lack of evidence . According to ANSES, however, a classification in the second category (suspected carcinogenic effects in humans) could possibly be justified, which ANSES did not examine. It therefore called on ECHA for an assessment.

In April 2016, the USEPA published the assessment of the carcinogenic potential of glyphosate by its Cancer Assessment Review Committee (CARC) from October 2015. Accordingly, glyphosate is probably not carcinogenic to humans. According to USEPA, the IARC rating ignored a number of studies with negative results. In addition, the studies cited by the IARC with positive results had decisive shortcomings and were not reproduced. The USEPA removed the CARC rating a few days after publication and announced a revision by the end of 2016. In September 2016, the CARC assessment was published again as part of the publication of the routine approval review (see above).

The New Zealand EPA published an assessment of the carcinogenic potential of glyphosate in August 2016. Based on the weight-of-evidence method and taking into account the quality and reliability of the available data, glyphosate is therefore unlikely to be genotoxic or carcinogenic to humans.

A review published in 2016 compiled the assessments of four independent expert groups regarding the carcinogenic potential of glyphosate and compared them with the IARC assessment. The expert groups concluded that the existing data did not justify the IARC rating of glyphosate as "likely to be carcinogenic" and that glyphosate is unlikely to pose a cancer risk to humans.

The APVMA published its position in September 2016 regarding a possible re-evaluation of glyphosate in response to the IARC assessment. The APVMA comes to the conclusion that glyphosate exposure is neither carcinogenic nor genotoxic. APVMA also sees no scientific evidence of harmful effects on humans or unintended negative effects on animals, plants and the environment from glyphosate or glyphosate-based pesticides. Therefore, a formal reassessment is not justified.

The Swiss Center for Applied Human Toxicology and the Ecotox Center jointly published an information sheet in March 2017 in which they explain the deviation of the IARC assessment from that of the BfR, EFSA and JMPR with several factors: In contrast to other organizations, IARC takes into account the regulatory data of the Manufacturers did not, interpreted and weighted the study situation differently and re-evaluated studies. As required by EU law, the BfR and EFSA only assessed the active ingredient glyphosate itself. The IARC assessment also takes various formulations into account, i. H. the admixtures that are regularly added to the active ingredient glyphosate. A discussion arose as to whether it was less the active ingredient glyphosate than the product admixtures that could cause the carcinogenic effect.

In California , the competent authority for health and the environment (OEHHA) announced on June 26, 2017 that glyphosate would be added to the list of chemicals that are carcinogenic from July 7 (Proposition 65). Monsanto had previously lost the Monsanto v OEHHA litigation . California law stipulates that chemicals that are classified as carcinogenic by the IARC must be listed under Proposition 65. However, the OEHHA will simultaneously announce No Significant Risk Levels (NSRLs) as soon as the relevant product warnings are required by law.

In 2019, the EPA, as the higher-level authority, revoked the requirement to mark a possible cancer risk (warning) for California. According to the EPA, it is "irresponsible to demand incorrect labeling when the EPA knows that there is no risk of cancer." This measure is intended to prevent the public from being "misled".

Court judgment of August 2018

In August 2018, a US court sentenced the glyphosate manufacturer Monsanto to pay damages of 289 million dollars (around 250 million euros). The plaintiff was a caretaker suffering from cancer who attributed his illness to years of use of weedkillers containing glyphosate. The jury justified its decision with the fact that Monsanto had not warned explicitly enough that there was a risk of cancer for humans through the weed killer, as the company has so far denied this risk.

In September 2018 Monsanto submitted objection against the court verdict one. The hearing on this took place on October 10, 2018. The verdict was upheld in the second instance, but the amount of damages was reduced significantly from $ 289 million to $ 78 million for formal reasons. Bayer submitted appeal against the judgment.

Court judgment of March 2019

The Federal District Court of California sees in its judgment of March 20, 2019 a "significant factor" in the development of the plaintiff's cancer. Bayer appealed.

Court judgment of May 2019

In May 2019, a California court sentenced the manufacturer Bayer to pay $ 2.05 billion in damages and additional penalties because the weed killer was carcinogenic and Bayer had not given sufficient warning. The amount was later reduced to 86.7 million and Bayer appealed.

Comparison from June 2020

In June 2020 it became known that Bayer had reached a settlement with a large number of the approximately 125,000 plaintiffs in the United States . Thereafter, Bayer will have to pay up to $ 10.9 billion. After the competent federal judge signaled that he would reject the settlement in its present form, Bayer, in agreement with the plaintiff's attorneys, withdrew the application for settlement in order to gain time for further clarification.

Teratogenicity and other diseases

A review published in 2011 examined epidemiological studies of glyphosate and diseases other than cancer combined: respiratory disease , diabetes , heart attack , reproductive and developmental disorders , rheumatoid arthritis , thyroid disease , and Parkinson's disease . The review found no evidence of a causal relationship between glyphosate exposure and any of these diseases.

A review published in 2012 summarized epidemiological studies, animal studies, and studies that examined the mechanisms of a possible causal relationship between glyphosate and reproductive and developmental disorders. There was no consistent effect from glyphosate exposure in the data. Also, no plausible mechanism has been clarified. Toxicity has been observed in some studies on mixtures with other substances, but there is strong evidence that these toxic effects are related to other substances, not glyphosate. The review also looked at glyphosate exposure and found extremely low levels. The estimated exposure was more than 500 times lower than the USEPA reference oral dose. The review concludes that there is no solid evidence for a link between glyphosate and reproductive and developmental disorders in realistic exposure scenarios.

A systematic review of observational studies published in 2016 that examined a possible connection between glyphosate exposure and teratogenicity (including in the context of GM soy cultivation in South America) concluded that, according to the current state of epidemiological knowledge, there is no evidence of a teratogenic potential glyphosate-based pesticides exist, although a connection cannot be definitely ruled out due to methodological weaknesses of observational studies.

Controversy surrounding Paganelli et al. , 2010 (teratogenicity)

In an Argentine study led by Andrés Carrasco it was shown that glyphosate-based herbicides (GBH) in sufficient concentrations can cause neural crest defects and craniofacial malformations in clawed frogs and chicken embryos. The study describes a match between the malformations found under laboratory conditions and malformations in people exposed to glyphosate during pregnancy.

The results published in the journal Chemical Research in Toxicology were the subject of EU deliberations in 2010. After the Federal Office for Consumer Protection and Food Safety for Germany had written an assessment of the study, which the other member states followed, the EU Commission came to the conclusion that that the study is of no relevance to the current risk assessment of glyphosate and GBH for humans. The reasons given are:

• For clawed frog and chicken embryonic development in water or in (chicken) eggs, due to considerable toxicokinetic differences, conclusions cannot be drawn about embryonic development in utero . More suitable studies in rats and rabbits did not provide any evidence of a teratogenic potential of glyphosate.
• The exposure route of co-cultivation of clawed frog eggs with GBH, injection of glyphosate into clawed frog embryos, and injection of GBH into chicken eggs is highly artificial and completely irrelevant for a risk assessment for humans. Human exposure would primarily be through skin and respiration.
• In numerous available developmental toxicity studies in mammals, no evidence of teratogenicity was found even at high doses tested.
• There are no epidemiological studies showing a connection between exposure to glyphosate and an increased incidence of teratogenic effects.

Monsanto said the results were not surprising given the method used and unrealistic exposure scenarios. In a study from 1985, for example, malformations caused by caffeine were found using the same method. According to Monsanto, this method is not relevant to human health effects, nor is it used by regulatory authorities.

In 2011, the journal published three letters to the editor, which criticized the method used and the interpretation of the results. Carrasco defended the study in a reply.

Effects on animals

Monika Krüger and her team established a possible connection between glyphosate and visceral botulism through disorders of the intestinal flora ( dysbiosis ) in several studies from 2013 to 2015 . According to a statement by the BfR from 2012, there was no empirical evidence for this until then. In the Ames test with Salmonella and E. coli, which is used to investigate mutagenicity , no antibacterial effect on the two species could be determined as a secondary finding, even at high concentrations . Feeding experiments with rodents, cows, dogs and goats could not identify any long-term disease symptoms that indicate a disruption of the intestinal flora.

The acute oral LD ₅₀ for the Virginia quail is 4971 mg ae / kg for glyphosate acid and 1742 mg ae / kg for glyphosate in a Roundup formulation. In the 8-day feeding test, the LC ₅₀ in quail and mallard was determined to be> 4640 mg / kg feed. Long-term feeding studies (20 weeks) with mallards and Virginia quails showed no harmful effects below 1000 mg ae glyphosate / kg feed. For the smaller Virginia quail this corresponds to a daily intake of 93 mg per kilogram of body weight. The acute oral LD _{50 determined} for the rat was 4275 mg ae / kg body weight (ae for acid equivalent) for glyphosate acid and 1550 mg ae / kg for the original Roundup product (MON 2139).

For honey bees , the lethal dose for ingestion with food is 100 µg ae glyphosate / bee, in direct contact with the spray solution it is> 100 µg ae / bee. When compared with the usual application rates, glyphosate only poses a low risk of damage to bees. However, as early as 2015 there were indications that non- lethal doses disrupt orientation.

According to a US study published in 2018 by Nancy Moran's working group , glyphosate changes the composition of the intestinal flora of young bees even at normal concentrations by inhibiting the shikimic acid pathway in some bacteria ( Snodgrassella alvi ) , with the result that changes in the intestinal flora affect digestion impaired and the immune system weakens and makes the animals, among other things, more sensitive to a harmful pathogen ( Serratia marcescens ), which increased their mortality in the experiment. The scientists suspect that honey bees are more susceptible to environmental stressors.

Earthworms are differently sensitive to glyphosate depending on the species. When Earthworm the LD is ₅₀ more than in 2300 and 1550 mg ae / kg soil for glyphosate or Roundup. The NOEC for the compost worm was determined to be 118.7 mg ae / kg. For other earthworm species occurring in agricultural soils, a study published in August 2015 showed that the dewworm ( Lumbricus terrestris ) almost completely ceased its activity after the application of glyphosate, while the meadow worm ( Allolobophora caliginosa ) remained unabated. The use of glyphosate also led to a 56% reduction in the reproduction rate of the meadow worm.

Fish are more sensitive to glyphosate. The LC ₅₀ (96 hours) was found to be 86 mg / l of water in trout and 120 mg / l in sunfish. Scientists at Monsanto give the lowest LC ₅₀ determined for a fish species to be 1.7 mg ae / l.

A study from 2010 investigated in the New Zealand freshwater fish Galaxias anomalus how infestation with the parasitic nugget worm Telogaster opisthorchis, with and without glyphosate exposure, affected life expectancy and malformations of the spine in its youth . When the fish were exposed to either glyphosate or the worm, no differences in life expectancy were found. Significantly lower survival rates resulted from infestation with the suction worm and simultaneous exposure to glyphosate. The spinal cord malformations were not significantly more pronounced in the presence of both stressors than in the case of suction worms alone.

Actually observed exposure values ​​are well below the lowest lethal concentrations. The maximum exposure value measured in a study of 51 bodies of water in the American Midwest in 2002 was 8.7 µg ae / l and 95% of the values ​​were between 0.45 and 1.5 µg ae / l. At 30 locations in southern Ontario investigated in 2004 and 2005, the maximum observed exposure value was 40.8 µg ae / l. In wetlands with known amphibian populations, the values ​​were typically below 21 µg ae / l.

Effects on fungi and microorganisms

In soil bacteria, the nitrification and hydrolysis of urea are the most sensitive processes to glyphosate; they are inhibited at concentrations of more than 5 mg ae / kg soil. Glyphosate increases the infestation with root fungi ( Fusarium , a parasitic harmful fungus especially in grain and maize) and prevents the accumulation of nodule bacteria .

According to Monsanto scientists, glyphosate has only a minor effect on the growth of many types of fungi under laboratory conditions. In contrast, a fungicidal effect of glyphosate was found in the obligate parasitic fungi brown rust of wheat , yellow rust and the Asian soybean rust on glyphosate-resistant plants.

Studies from 1985 and 1989 came to the conclusion that glyphosate impaired the radial growth of selected mycorrhizal fungi . Plants that rely on mycorrhiza are particularly sensitive to the active ingredient glyphosate. This was found, for example, for the rose family and explicitly for the genus Sorbus . A study from 2014 found that after treatment with a herbicide containing glyphosate, the mycorrhization of the roots and mycorrhizal structures in the soil (spores, vesicles, expansion units) were significantly reduced. Since around 80% of all plants are associated with symbiotic mycorrhizal fungi and are of great importance for their nutrient uptake, indirect effects on the nutrient balance in these ecosystems are to be expected.

Hormesis

In low doses, glyphosate can have stimulating effects on plants ( hormesis ). Studies with several species of different botanical categories showed hormetic effects at doses from 1.8 to 25 g ae (= acid equivalent , German  acid equivalent ) per hectare. The proven effects include, for example, an acceleration of the electron transport chain and carbon dioxide assimilation , higher yield and increased biomass quality. However, hormetic and phytotoxic doses are close together and are dependent on the environment, which makes it difficult to use glyphosate to increase yield. The hormetic effects are usually short-lived, and increases in yield under field conditions have only rarely been demonstrated. Glyphosate-resistant plants show no hormetic effects. The mechanisms underlying such a hormesis are not known.

Indirect and systemic environmental impacts

Support of conservation tillage

The combination of glyphosate application and conservation tillage ( no-till tillage ) often leads to economic advantages. Since the time-consuming plowing is dispensed with, conservation tillage requires less manpower and energy under suitable circumstances, soil erosion and harmful soil compaction are reduced and soil moisture is better preserved. A typical disadvantage here is increased weed pressure, which significantly increases the use of herbicides.

The German Federal Environment Agency issued a press release in January 2014, in which it linked the large-scale application of glyphosate to a restriction of biological diversity . However, an effective (no-till) weed control could also be through a variety of crop rotation , intercropping and harrows realize, and thus reduce the discharged of glyphosate.

Together with glyphosate-tolerant soybeans, Glyphosat Perry et al. (2016), the spread of conservative tillage in the USA increased by 10-20% in the period 1998-2011.

Effects of replacing other weed control measures

The use of glyphosate-resistant plants has generally increased the use of glyphosate and decreased the use of other herbicides. Glyphosate is, on average, more environmentally friendly than the herbicides it replaces. Glyphosate binds to the soil faster, which reduces the risk of leaching. Glyphosate is biodegraded by soil bacteria, and its toxicity to mammals, birds and fish is low. In contrast to other herbicides, glyphosate is only detectable in the soil for a relatively short time. Estimates of the environmental effects of replacing other herbicides were made using the Environmental Impact Quotient (EIQ) by Brookes and Barfoot in the context of a study initiated by Monsanto. According to these estimates, the average amount of herbicidal active ingredient used in the cultivation of glyphosate-resistant plants decreased in most countries compared to the cultivation of non-glyphosate-resistant plants and the substitution led to a lower environmental impact (also in isolated cases in which the amount of herbicidal active ingredient increased). In the cultivation of glyphosate-resistant plants, the use of glyphosate and other herbicides has increased in recent years due to increasing problems with glyphosate-resistant weeds. Nevertheless, according to the authors' estimates, the environmental profile of the use of herbicides in the cultivation of glyphosate-resistant plants remained more favorable than in the cultivation of non-glyphosate-resistant plants. Brookes and Barfoot (2014) estimate that between 1996 and 2012, a total of 242.55 million kg of herbicidal active ingredients were saved worldwide through the cultivation of herbicide-tolerant (predominantly glyphosate-resistant) plants, of which 203.2 million kg were in maize. The EIQ of herbicide use decreased in all plants and in all countries examined (to varying degrees).

According to the JKI impact assessment (2015) of the renouncement of glyphosate in Germany, only chemical alternatives that have less favorable ecotoxicological properties are permitted in apple cultivation. With the exception of the active ingredient deiquat for siccation in rapeseed, no chemical alternative could be identified for arable farming . According to the JKI, the non-chemical alternatives also have negative environmental effects. In particular with regard to the indirect effects on biodiversity via trophic interactions, only minor differences between non-chemical weed control and the use of glyphosate are to be expected on the target areas. With regard to other effects - such as ecotoxicological aspects with regard to amphibians and algae against soil life and erosion - the impact assessment cannot make a final assessment.

Glyphosate-resistant weeds

Amaranthus palmeri is one of the best-known glyphosate-resistant weeds

In the same way as with other herbicides, the continuous and unilateral use of glyphosate can encourage the development of resistant weeds . In the public debate glyphosate are (GR) weeds sometimes (as "super weeds" English superweed ), respectively. Today there are fewer weeds that are resistant to glyphosate than to some other herbicides. However, due to the widespread use of glyphosate, the effects of GR weeds are significant, especially for glyphosate tolerant (GT) crops.

The number of GR weeds grew slowly until 2003, but faster thereafter. In mid-2017, 38 GR weeds were known, 17 of them in the USA. In the USA, GR weeds occur particularly frequently in GT maize, GT soy and GT cotton and are favored by the typical crop rotation GT soy - GT maize.

Against this background, measures are recommended that reduce the selection pressure on weeds, and broader weed control is recommended. Genetic innovations, novel full-dose herbicide mixtures and alternatives to glyphosate are named as possibilities . Mechanical and precision farming methods as well as crop cultivation practices such as planting and crop rotation planning are recommended in order to reduce the dependence on glyphosate. This is necessary so that the benefits of glyphosate can continue to be used in the future.

regulation

Europe

European Union

The use of glyphosate is permitted in the EU. The permitted daily dose (ADI) is 0.5 and the acceptable user exposure 0.1 milligrams per kilogram of body weight and day.

Limit values ​​for maximum residue levels in food are always related to an active ingredient / culture combination and take into account the respective type of application. For glyphosate, different maximum residue levels are set depending on the crop and type of application. The maximum residue level for use as a means of combating wild herbs in cereal crops, for example for buckwheat and rice, is 0.1 mg per kilogram of crop. If glyphosate is used for pre-harvest treatment ( siccation ), a maximum residue content of 10 mg per kilogram of harvested material applies to wheat and rye, i.e. a value that is 100 times higher than that of other types of grain.

The current EU approval was granted in 2002 and was originally due to expire on December 31, 2015. As part of the routine review of the approval of active ingredients in plant protection products , the Federal Institute for Risk Assessment (BfR) completed the health risk assessment in December 2013. The analysis of numerous new documents did not reveal any evidence of carcinogenic, reproductive or teratogenic effects due to glyphosate in experimental animals. It gave no reason to change the health limit values ​​significantly. In February 2015, the revised assessment report of the Federal Institute for Risk Assessment (BfR) on the health assessment of glyphosate was presented at an expert meeting at the European Food Safety Authority (EFSA). The report was then supplemented one more time by the BfR. This revision includes a. Newly added rating tables and editorial additions to clarify some issues. The BfR sent this amended, revised version of the report to the Federal Office for Consumer Protection and Food Safety (BVL) on April 1, 2015 for forwarding to EFSA, thus completing its preparatory work in the EU approval procedure.

In March 2014, EFSA announced the BfR reassessment of glyphosate and gave the opportunity to comment publicly until May 11, 2014. On October 20, 2015, the EU Commission extended the approval, which was originally valid until the end of 2015, to June 30, 2016, as the reassessment was delayed for reasons over which the applicants had no influence. On November 12, 2015, EFSA published the summary of the toxicological assessment of glyphosate. After no qualified majority for or against a new authorization was reached in the responsible committees of representatives of the EU member states , the commission extended the authorization in June 2016 for a further 18 months until the end of 2017.

In January 2017, the EU Commission announced the adoption of a European Citizens' Initiative (ECI) supported by the organizations WeMove, Campact, Global 2000 and Greenpeace . This should propose to the EU Commission to submit a glyphosate ban to the member states and to revise the approval procedures for plant protection products., Since the required number of signatures has been reached, the EU Commission is required to respond by January 8, 2018.

The EU member states moved on 25 October 2017 vote on a renewal of glyphosate. The EU Commission had proposed a ten-year extension for which there was no majority among the EU countries. In the responsible expert committee of the member states, a revised proposal by the EU Commission to renew the approval for five years found neither a qualified majority for nor against on November 9th.

On November 27, a qualified majority of the EU countries finally agreed to an extension of the approval for a further five years. While 18 member states, including Germany, which had so far always abstained, approved the EU Commission's proposal, nine countries (France, Italy, Belgium, Austria, Greece, Cyprus, Malta, Croatia and Luxembourg) voted against. Portugal was the only country to abstain.

With his approval, the German Agriculture Minister Christian Schmidt (CSU), allegedly without consulting the Chancellor, disregarded the rules of procedure of the federal government; because Environment Minister Barbara Hendricks ( SPD ) had not approved a further approval. According to the usual procedure, Germany should have abstained because the two ministers involved in the decision had different opinions.

Andrea Nahles (SPD) called this process, which took place in the run-up to the talks for a possible grand coalition after the election to the 19th Bundestag, a “serious breach of trust”. The Greens demanded Schmidt's resignation, the FDP questioned the ability to form a coalition.

Denmark

In Denmark , the use of glyphosate to accelerate ripening (siccation) is prohibited from the 2018 harvest.

Germany

As of October 24, 2017, 100 plant protection products containing glyphosate are approved in Germany.

Compliance with limit values ​​for glyphosate residues in food is controlled by the official food control. Of the 1112 samples examined nationwide in 2011, 1066 (95.86%) were free of residues (below the detection limit ). Of the 4.13% of the samples with residues (measured values ​​above the detection limit), around three quarters were complained about because of values ​​above the maximum level.

In the past, the BVL asked the authorization holders of the relevant plant protection products to replace the polyethoxylated alkylamines with other wetting agents. According to the BfR, this exchange has already taken place.

In May 2014, the Federal Office for Consumer Protection and Food Safety (BVL) set an immediately applicable limit on glyphosate and products containing glyphosate. In a calendar year, plant protection products containing glyphosate may only be applied to the same area no more than twice and at least 90 days apart. The amount of active ingredient must not exceed 3.6 kg per hectare and year. The late application in cereals is limited to those parts of the area where weed growth makes harvesting impossible. The use for siccation is only allowed if harvesting without treatment is not possible (if grain ripens unevenly); use to control the harvest date is prohibited.

The Federal Office for Consumer Protection and Food Safety has specified suitable protective clothing and protective gloves for the application in its application regulations.

The Bavarian dairy cooperative Milchwerke Berchtesgadener Land Chiemgau became the first large dairy in Germany to prohibit its suppliers from using glyphosate on October 25, 2017. This decision was passed unanimously by the Supervisory Board.

Protest banners against the use of glyphosate as a weed killer in Bremm on the Moselle

The federal government intends (as of February 2020) “to significantly restrict the use of glyphosate by amending the Plant Protection Application Ordinance. The aim is for private gardens to come into force as soon as possible in 2020. ”An initiative by Environment Minister Hendricks in 2017 failed due to resistance from Agriculture Minister Schmidt . The Federal Minister for the Environment, Nature Conservation and Nuclear Safety , Svenja Schulze , is aiming for a ban for agricultural companies from 2023 as well. According to the Federation for the Environment and Nature Conservation Germany (BUND), 181 German municipalities refrain from using glyphosate when maintaining their green and open spaces.

On September 4, 2019, the Federal Ministry for the Environment, Nature Conservation and Nuclear Safety decided on the extensive "Action Program for Insect Protection". Stricter rules for the use of pesticides should also serve to preserve the biodiversity of insects: "With a systematic reduction strategy from 2020, the federal government will significantly limit the use of glyphosate-containing and equally effective pesticides by changing the Plant Protection Application Ordinance and completely end the use of glyphosate-containing pesticides by 2023 . “The decision was based on the loss of biodiversity.

Austria

As of October 24, 2017, 49 herbicides containing glyphosate are approved in Austria. In response to the Brussels resolutions of November 28, 2017, the SPÖ tried to propose a law for a national glyphosate ban in the newly elected National Council.

Since November 29, 2017, dairy farmers of several brands of the Berglandmilch dairy ( Schärdinger , Tirol Milch and Stainzer Milchbauern ) are no longer allowed to use glyphosate. According to Greenpeace , almost a quarter of the municipalities in Austria refrained from using glyphosate in April 2018. In Carinthia , use on public areas has been prohibited since February 1, 2018. The total ban adopted in Carinthia in December 2017 was overturned by the EU Commission in March 2018. In December 2018 it became known that Carinthia wanted to impose a ban on private use. The amendment to the law should be passed in the state parliament by the end of January 2019 at the latest .

Portugal

By March 2018, 12 district towns ( Concelhos ) and 20 municipalities ( Freguesias ) have made a binding commitment not to use glyphosate in municipal green spaces and companies (nurseries, tree nurseries, etc.) and to promote their avoidance in the district or municipality, including cities such as Porto , Braga or Funchal , capital of Madeira Island . Some municipalities in the capital Lisbon also joined, such as Estrela .

France

French President Emmanuel Macron intends to take glyphosate off the market by 2021. On January 15, 2019, the Lyon Administrative Court revoked the approval for the product Roundup Pro 360, a special weed killer containing glyphosate. The court relied on the precautionary principle enshrined in the French constitution and relied on scientific studies and animal experiments which had shown that the overall composition of this formulation was more toxic than the active ingredient glyphosate itself. In March 2017, Roundup Pro 360 was approved by the Agence nationale de sécurité sanitaire de l'alimentation, de l'environnement et du travail (Anses).

Switzerland

The Federal Office for Agriculture is responsible for approval in Switzerland ; Assessment bodies are also the Federal Food Safety and Veterinary Office , the Federal Office for the Environment and the State Secretariat for Economic Affairs . On October 4, 2017, over 100 herbicides containing glyphosate were approved. In contrast to the EU, siccation with herbicides is prohibited in Switzerland. A motion by the Green Party to ban glyphosate until at least 2022 was rejected by the Federal and National Council. A postulate of a study by the authorities to determine the modalities for a possible phasing out of the use of glyphosate was supported by the Federal Council with regard to international uncertainties. In 2017, the federal government wanted to increase the limit values for glyphosate in the Water Protection Ordinance from 0.1 to 10 micrograms (μg) per liter of water. After criticism in the consultation , DETEC decided against increasing the existing limit value.

America

Brazil

In August 2018, a Brazilian court banned the use of glyphosate pending a government decision.

Colombia

In May 2015, the Colombian government announced that it would completely stop spraying glyphosate. It justified this step with a reference to health risks and the re-evaluation of glyphosate by the WHO as "probably carcinogenic".

United States of America

The U.S. Environmental Protection Agency (EPA) has published a draft glyphosate assessment that assessed both human health and environmental risks. The draft concludes that glyphosate is unlikely to be carcinogenic to humans. On December 18, 2017, the EPA announced that it would take sixty days to comment on the draft. In 2019, the EPA has to decide whether to extend the approval of glyphosate in the USA.

Controversies about use in Latin America

Argentina

According to the Süddeutsche Zeitung, 41 times as much cancer was diagnosed among the 6000 inhabitants in the village of Ituzaingó Anexo near Córdoba than the Argentine average. Since the village is close to fields that have been treated with pesticides by agricultural aircraft, residents and environmental groups such as the Mothers of Ituzaingó , founded by Sofía Gatica , suspect that glyphosate is the cause. In 2012, a pilot and two soy producers were found guilty by a court of spraying glyphosate and endosulfan near residential areas around Cordoba . In addition, the highest court in Argentina has generally established safety distances to residential areas where spraying is not allowed, and the burden of proof in damages proceedings has been reversed in favor of the plaintiffs.

The city council of Rosario , the third largest city in Argentina, has banned the use of glyphosate in fields, public spaces and private gardens in and around the city. On December 27, 2017, this ban was published in Regulation 9798 in the Official Journal.

Colombia

The Colombian police use glyphosate in combination with the wetting agent Cosmo-Flux to destroy coca and opium poppy plantations with spray planes as part of the national drug fight ( Plan Colombia ) . The population living in the spray area has reportedly experienced various symptoms of the disease. According to a study by Keith R. Salomon and others published in 2007, this spraying of the glyphosate / Cosmo-Flux combination does not pose a significant risk to human health. Its use is insignificant for terrestrial mammals and birds. There could be moderate risks to aquatic organisms in shallow waters if the application is overdosed. Elements of coca production, such as slash and burn , pesticide use and expulsion of flora and fauna are far more relevant risks to health and the environment than the use of glyphosate.

In connection with the spraying, skin and eye problems, infections of the respiratory tract , stomach and intestinal diseases and fever were found in the population living in the spray area . Symptoms that indicate overstimulation of the central nervous system were mainly observed immediately after the spraying . These symptoms manifested themselves in particular in headache , dizziness, stomach pain and general weakness. As the main spraying area is in the border area between Colombia and Ecuador , diplomatic tensions arose over the consequences of the spraying. For example, the Ecuadorian government demanded that the Colombian government maintain a 10-kilometer protective radius from the San Miguel river when spraying. In the context of a binational seminar in 2001, the Colombian delegation promised to take a protective radius into account. However, a commission of inquiry found in 2002 that this was not being observed.

Ecuador finally sued Colombia in 2008 before the International Court of Justice in The Hague and reached a settlement with Colombia on September 9, 2013.

Movies

• In the US, cancer patients are suing Monsanto. Video report , 7:02 min., Nano ( 3sat ) on November 9, 2017 ( online )
• Roundup, the process. Documentary, France 2017, 90 min, Director:. Marie-Monique Robin , production: M2R film co-production: Arte ( Summary ( Memento of 8 December 2017 in the Internet Archive ) and online video )
• Back to the field. Video report, 4:07 min., Nano (3sat) on March 16, 2017 ( online )
• Poison in the field - glyphosate, the underestimated danger? Documentary, Germany 2015, 42:50 min., Script and direction: Volker Barth and Susanne Richter, production: WDR , series: die story ( table of contents and online video ); The film was awarded the Salus -Medienpreis Grand Prize 2016 awarded
• Dead animals - sick people. Documentary, Germany, 2015, 45 min., Script and direction: Andreas Rummel, production: Rumara Fernsehproduktion UG on behalf of MDR in collaboration with Arte ( online )
• How dangerous is glyphosate ?. Video report, 4:27 min., W wie Wissen ( ARD ) on September 8, 2013 ( online )

literature

• Helmut Burtscher Damage: The Glyphosate File. How corporations use the weaknesses of the system and thereby endanger our health . Kremayr & Scheriau , 2017, ISBN 978-3-218-01085-6

Web links

Commons : Glyphosate  - collection of images, videos, and audio files

• Federal Ministry for the Environment, Nature Conservation and Nuclear Safety : Frequently asked questions about glyphosate
• Federal Food Safety and Veterinary Office : Glyphosate
• (Eco) toxicological assessment of glyphosate - debate about a plant protection product , information sheet from SCAHT and the Ecotox Center

Individual evidence

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3. ↑ Entry on glyphosate in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on May 15, 2017. Manufacturers or distributors can expand the harmonized classification and labeling .
4. ↑ ^{a b c} National Pesticide Information Center , Technical factsheet ( PDF )
5. ↑ ^{a b c} Entry on glyphosate. In: Römpp Online . Georg Thieme Verlag, accessed on October 27, 2017.
6. ↑ ^{a b c d e f} Stephen O. Duke, Stephen B. Powles (2008): Mini-review Glyphosate: a once-in-a-century herbicide . Pest Management Science 64, pp. 319-325, doi: 10.1002 / ps.1518 .
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12. ↑ Industry co-finances glyphosate studies. Retrieved December 5, 2019 . 
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24. ↑ Water quality - determination of glyphosate and AMPA - method using high-performance liquid chromatography (HPLC) and fluorometric detection: ISO 21458: 2008-12 - Beuth.de .
25. ↑ Water quality - determination of glyphosate and AMPA - method using high-performance liquid chromatography (HPLC) with tandem mass spectrometric detection: ISO / DIS 16308: 2013-02 - Beuth.de .
26. ↑ Y. Nagatomi, T. Yoshioka, M. Yanagisawa, A. Uyama, N. Mochizuki: Simultaneous LC-MS / MS analysis of glyphosate, glufosinate, and their metabolic products in beer, barley tea, and their ingredients. In: Bioscience, Biotechnology, and Biochemistry. 2013, 77 (11), pp. 2218-2221, doi: 10.1271 / bbb.130433 , PMID 24200782 .
27. ↑ Steinborn A, Alder L, Michalski B, Zomer P, Bendig P, Martinez SA, Mol HG, Class TJ, Pinheiro NC: Determination of Glyphosate Levels in Breast Milk Samples from Germany by LC-MS / MS and GC-MS / MS . , J Agric Food Chem. 2016 Feb 17; 64 (6): 1414-21, PMID 26808680
28. ↑ Connolly A, Basinas I, Jones K, Galea KS, Kenny L, McGowan P, Coggins MA: Characterizing glyphosate exposures among amenity horticulturists using multiple spot urine samples. , Int J Hyg Environ Health. 2018 Aug; 221 (7): 1012-1022, PMID 30078418
29. ↑ Thompson TS, van den Heever JP, Limanowka RE: Determination of glyphosate, AMPA, and glufosinate in honey by online solidphase extraction-liquid chromatography-tandem mass spectrometry. , Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2019 Feb 26: 1-13, PMID 30806173
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37. ↑ Yoshito Kamijo, Michiko Takai, Tetsuya Sakamoto: A multicenter retrospective survey of poisoning after ingestion of herbicides containing glyphosate potassium salt or other glyphosate salts in Japan . In: Clinical Toxicology . tape 54 , no. 2 , 2016, p. 147-151 , doi : 10.3109 / 15563650.2015.1121271 .
38. ↑ see R. Mesnage, B. Bernay, G.-E. Séralini: Ethoxylated adjuvants of glyphosate-based herbicides are active principles of human cell toxicity . In: Toxicology . tape 313 , no. 2–3 , 2013, pp. 122-128 , doi : 10.1016 / j.tox.2012.09.006 .
39. ↑ Rick E. Relyea: The lethal impact of Roundup on aquatic and terrestrial amphibians . In: Ecological Applications . tape 15 , no. 4 , 2005, p. 1118-1124 .
40. ↑ ^{a b c} Werner Perkow: Active substances in pesticides and pesticides . 2nd Edition. Paul Parey Publishing House, 2nd supplement in March 1988.
41. ↑ AS Culpepper, TL Gray, WK Vencill, JM Kichler, TM Webster, SM Brown et al .: Glyphosate-resistant Palmer amaranth (Amaranthus palmeri) confirmed in Georgia. Weed Sci. Volume 54, 2006, pp. 620-626, doi: 10.1614 / WS-06-001R.1 .
42. ^ Sarah C. Wynn, Sarah K. Cook, James H. Clarke: Glyphosate use on combinable crops in Europe: implications for agriculture and the environment . In: Outlooks on Pest Management . tape 25 , no. 5 , 2014, p. 327–331 , doi : 10.1564 / v25_oct_07 .
43. ↑ ^{a b} Julius Kühn Institute, Federal Research Institute for Cultivated Plants (editor) (2017): Recommended action by the federal-state expert group on the use of glyphosate in arable farming and grassland management. Reports from the Julius Kühn Institute Volume 187. 11 pages. doi: 10.5073 / berjki.2017.187.000 (open access).
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46. ↑ Europe-wide study shows pesticides in urine in the standard of June 13, 2013.
47. ↑ Horst Henning Steinmann, Michael Dickeduisberg, Ludwig Theuvsen: Uses and benefits of glyphosate in German arable farming. In: Crop Protection. Volume 42, 2012, pp. 164-169, doi: 10.1016 / j.cropro.2012.06.015
48. ↑ ^{a b} Hella Kehlenbeck, Jovanka Saltzmann, Jürgen Schwarz, Peter Zwerger, Henning Nordmeier, Dietmar Roßberg, Isabella Karpinski, Jörn Strassemeyer, Burkhard Golla, Bernd Freier: Impact assessment for agriculture on the partial or complete waiver of the use of glyphosate-containing herbicides in Germany . Julius Kühn Institute, Quedlinburg 2015, ISBN 978-3-95547-027-2 , p. 14-15 ( online ).
49. ↑ Conservation- appropriate maintenance on the track . deutschebahn.com.
50. ↑ Christian Schlesiger, Jürgen Salz: The shock therapy. Report by Wirtschaftswoche magazine in issue 25/2019 of June 14, 2019, pages 62–63 and online Weeds on the tracks: Deutsche Bahn's glyphosate dilemma
51. ↑ Weed killing: Deutsche Bahn wants to inject less glyphosate Report by Wirtschaftswoche magazine from August 30, 2019
52. ↑ Jürgen Salz: Controversial agricultural poison: Why glyphosate when hot water also helps? from September 30, 2019
53. ↑ Consumer information on glyphosate. In: Austrian Agency for Health and Food Safety GmbH. Austrian Agency for Health and Food Safety, April 25, 2018, accessed on November 7, 2018 . 
54. ↑ Carinthia bans glyphosate for private customers from March 28, 2019 in the press of March 19, 2019, accessed on April 14, 2019.
55. ↑ Austria decides total ban on glyphosate , Süddeutsche Zeitung, July 2, 2019.
56. ↑ Total ban on glyphosate decided orf.at, July 2, 2019, accessed on July 2, 2019.
57. ↑ Clear the way for domestic glyphosate ban on ORF from December 2, 2019, accessed on December 6, 2019.
58. ↑ Formal error: Austria does not implement planned glyphosate ban on aerzteblatt.de from December 10, 2019, accessed on January 17, 2020.
59. ↑ Federal Office for Agriculture : Sales statistics for plant protection products in Switzerland , July 24, 2018.
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73. ↑ Pesticide Residues in Food: 4.10 Glyphosate (158). FAO, 2005.
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77. ↑ National Breastfeeding Commission and BfR recommend mothers to continue breastfeeding . BfR, June 30, 2015.
78. ↑ BfR study confirms: no glyphosate detectable in breast milk . BfR, February 11, 2016.
79. ↑ Angelika Steinborn, Lutz Alder, Britta Michalski, Paul Zomer, Paul Bendig, Sandra Aleson Martinez, Hans GJ Mol, Thomas J. Class, Nathalie Costa Pinheiro: Determination of Glyphosate Levels in Breast Milk Samples from Germany by LC-MS / MS and GC-MS / MS . In: Journal of Agricultural and Food Chemistry . tape 64 , no. 6 , 2016, p. 1414-1421 , doi : 10.1021 / acs.jafc.5b05852 .
80. ^ Zen Honeycutt, Moms Across America Henry Rowlands, Sustainable Pulse. Supporter: Lori Grace, Environmental Arts & Research: Glyphosate Testing Report: Findings in American Mothers' Breast Milk, Urine and Water , April 2014.
81. ↑ Michelle K. McGuire, Mark A. McGuire, William J. Price, Bahman Shafii, Janae M. Carrothers, Kimberly A. Lackey, Daniel A. Goldstein, Pamela K. Jensen, John L. Vicini: Glyphosate and aminomethylphosphonic acid are not detectable in human milk . In: The American Journal of Clinical Nutrition . 2016, p. 1-6 , doi : 10.3945 / ajcn.115.126854 .
82. ↑ US breast milk is glyphosate free. Retrieved July 29, 2015 . 
83. ↑ James S. Bus: Analysis of Moms Across America report suggesting bioaccumulation of glyphosate in US mother's breast milk: Implausibility based on inconsistency with available body of glyphosate animal toxicokinetic, human biomonitoring, and physico-chemical data . In: Regulatory Toxicology and Pharmacology . tape 73 , no. 3 , 2015, p. 758-764 , doi : 10.1016 / j.yrtph.2015.10.022 .
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