Petroleum in Pesticides: A Need to Change Regulatory Toxicology.

Toxicological investigations of pesticides largely focus on the declared active ingredient, which constitutes only between a few percent to around 50% of the total formulation. The complete formulations are unknown. For each declared active ingredient, there are dozens or hundreds of formulations. We demonstrate that petroleum has always been and is still always in pesticides. Gas chromatography and mass spectrometry (GC-MS) were applied for 24 pesticides. The measured compounds were the 16-priority polycyclic aromatic hydrocarbons (PAHs). The ratio of the PAHs to the threshold of toxicity was from 2.16 to 8288 times. The levels and distribution of PAHs per pesticide were different. Petroleum residues appear to be a waste product. The declared active component is taken alone for toxicity calculations, such as the acceptable daily intake (ADI). The PAHs with 2-3 cycles are more represented in pesticides than those with 4-6 cycles, which underlines that the petroleum residues appear to come mainly from crude unburned material. The ADI should be divided by 1000 if it is considered that petroleum residues amplify the toxicity by 1000. The admixture of PAHs in pesticides can be highly carcinogenic or toxic in the long term, even more than the declared active ingredient itself.

Dataset of pollutants in organic and non-organic food.

Organic and non-organic equivalent corresponding type of foods were assessed for pollutants, polycyclic aromatic hydrocarbons (PAHs), pesticides and heavy metals. In total, 35 samples of sausages and cheeses were tested from three western European countries, Spain, France, and Germany. These samples were chosen because they are meat and milk products presenting some bioaccumulation capacity. Petroleum residues were demonstrated in pesticide formulants. These include polycyclic aromatic hydrocarbons (PAHs) and metals. We measured in these human foods 800 pesticides, 24 PAHs, using accredited methods, as well as eleven metals and elements. Pesticides' measurements were performed either by gas or liquid chromatography, followed by mass spectrometry, according to regulatory standard methods, that were measured over the threshold of 10 µg/kg for this reason. This could be insufficient to detect all toxic contaminations. Metals were analysed by high frequency induced plasma emission spectrometry and mass spectrometry after pressurized digestion. PAHs were assessed by gas and/or high-performance liquid chromatography with reverse phase polarity and if necessary double mass spectrometry. The raw data are summarized in Tables 1 and 2. The dataset can be reused for statistical analyses by the scientific community to evidence food pollution and to be compared with other measurements.

A Glyphosate-Based Formulation but Not Glyphosate Alone Alters Human Placental Integrity.

Glyphosate (G)-based herbicidal formulations, such as the most commonly used one, Roundup (R), are major pesticides used worldwide on food and feed. Pregnant women may be frequently exposed to R compounds. These are composed of G, which is declared as the active principle, and other products contained in formulations, named formulants, which have been declared as inerts and diluents by the manufacturers. These formulants have, in fact, been demonstrated to be much more toxic than G, in particular to placental and embryonic human cells. In this work, we thus compared the effect of G and a GT+ formulation named R, using placental perfusion ex vivo. R, but not G alone, was demonstrated to alter the placental permeability of a known small model molecule, antipyrine. Similar results were observed for the fetal venous flow rate. The transfer of G alone increases with time, but is significantly decreased in presence of its formulants. The perfusion of R provokes a destruction of fetal vessels, as demonstrated by immunohistochemistry. Formulants obviously alter the fetal-placental circulation and placental integrity according to time of exposure. Therefore, G does not appear to be the main toxic agent of R. Formulants, although undeclared, include polyoxyethanolamines, PAHs, or heavy metals, and may be responsible for this toxicity. These compounds are also present in other pesticides. The progressive blood flow reduction due to the toxic compounds of formulations may diminish the nutrient supply to the fetus, alter the development, and may enhance the poisoning effects. Although these are preliminary results, they could at least partially explain some adverse pregnancy outcomes in mothers exposed to pesticides or other environmental pollutants. The debate on glyphosate alone is proven insufficient for the understanding of the toxicity.

Endocrine disruptors also function as nervous disruptors and can be renamed endocrine and nervous disruptors (ENDs).

Endocrine disruption (ED) and endocrine disruptors (EDs) emerged as scientific concepts in 1995, after numerous chemical pollutants were found to be responsible for reproductive dysfunction. The World Health Organization established in the United Nations Environment Programme a list of materials, plasticizers, pesticides, and various pollutants synthesized from petrochemistry that impact not only reproduction, but also hormonal functions, directly or indirectly. Cells communicate via either chemical or electrical signals transmitted within the endocrine or nervous systems. To investigate whether hormone disruptors may also interfere directly or indirectly with the development or functioning of the nervous system through either a neuroendocrine or a more general mechanism, we examined the scientific literature to ascertain the effects of EDs on the nervous system, specifically in the categories of neurotoxicity, cognition, and behaviour. To date, we demonstrated that all of the 177 EDs identified internationally by WHO are known to have an impact on the nervous system. Furthermore, the precise mechanisms underlying this neurodisruption have also been established. It was previously believed that EDs primarily function via the thyroid. However, this study presents substantial evidence that approximately 80 % of EDs operate via other mechanisms. It thus outlines a novel concept: EDs are also neurodisruptors (NDs) and can be collectively termed endocrine and nervous disruptors (ENDs). Most of ENDs are derived from petroleum residues, and their various mechanisms of action are similar to those of "spam" in electronic communications technologies. Therefore, ENDs can be considered as an instance of spam in a biological context.

Dataset of compounds in glyphosate-free herbicides.

We analysed 14 recently marketed pesticides for consumers, available in France, Germany, and Poland. They were supposed to be glyphosate-free herbicides; glyphosate was banned for sale to the public in 2019. Measurements of 36 metals, 16 polycyclic aromatic hydrocarbons, 6 essential minerals, and glyphosate plus aminomethyl phosphonic acid, were performed in a laboratory accredited for regulatory purposes. The technologies used were respectively inductively coupled plasma mass spectrometry, gas-chromatography coupled with mass spectrometry, and high-performance liquid chromatography. These data can be used by scientists, the public, and regulatory bodies.

Toxic compounds in herbicides without glyphosate.

Glyphosate has been banned in some herbicidal formulations. We analyse for the first time 14 marketed products in Europe where glyphosate was replaced by acetic, pelargonic, caprylic or capric acids, or even benzalkonium chloride, to be supposedly less toxic. 35 heavy metals, 16 polycyclic aromatic hydrocarbons (PAHs), and essential minerals were tested by specific mass spectrometry associated with gas chromatography or inductively coupled plasma methods in the formulations. Essential minerals do not reach toxic levels, but heavy metals are found at levels up to 39 mg/L, depending on the product, and include silicon, arsenic, lead, iron, nickel, and titanium. Their presence at up to several hundred times the admissible levels in water may be due to nanoparticles embedding pesticides. PAHs reach levels of 32-2430 µg/L in 12 of the 14 samples; for instance, the carcinogen benzo(A)pyrene was detected. It was found to be present at up to several thousand times above the norm in water, as was benzo(A)anthracene. These compounds did not add significant herbicidal effects. Low levels of glyphosate were detected in 2 samples. These variable levels of undeclared toxic chemicals violate European Union rules on pesticides and may have health and environmental consequences, especially when exposure is long-term.