Pesticides vs. Biopesticides: From Pest Management to Toxicity and Impacts on the Environment and Human Health.

The environmental pollution that occurs in direct response to the widespread use of man-made/conventional pesticides results from many chemicals that require a long period of time, often decades, to degrade. The synthetic nature of pesticides also harms animals, beneficial insects, microorganisms, and plants, as well as humans. Fortunately, however, there are many natural pesticides, the so-called biopesticides, that are also effective against pests and more importantly, do not interfere with the well-being of ecosystems. Consequently, most biopesticides are safer for use around people and pets than man-made pesticides because, for example, they can be easily washed away from fruits and vegetables. The natural habitat is a rich resource with a wide selection of plants, many of which are also used to treat diseases in humans, animals, and plants. Out of concern for public health, environmental safety, and the stringent regulation of pesticide residues in agricultural commodities, the use of biopesticides is becoming increasingly important, but questions regarding potential pest resistance to these products may arise, just as is the case with conventional pesticides. Therefore, the performance and potential role of biopesticides in the management of plant pests should be prioritized due to their sustainability and importance to human and environmental welfare. In this review, we propose to highlight a scenario in which we discuss in detail the main constraints posed by the use of pesticides compared to biopesticides, starting with issues regarding their definition and continuing on to issues related to their toxicity and their impact on the environment and human health.

Intensification of the photodegradation efficiency of an emergent water pollutant through process conditions optimization by means of response surface methodology.

Heterogeneous photocatalysis has been increasingly investigated during the past years and has been recognized as a promising technique for clean and safe water purification. The current study exploits the advantage of this technique demonstrating that the removal of a biorefractory water pollutant named clofibric acid can be really improved by photocatalysis through a parametric comprehensive investigation and optimization study based on response surface methodology. Its novelty comes from the approach used to enhance the efficiency of the photocatalytic degradation of clofibric acid. A custom central composite design consisting of 49 trials was applied for process modeling and a quadratic robust model was derived based on the analysis of variance for the optimization of the process parameters. The effective removal of the target molecule with about 70% carbon mineralization was achieved under optimal photocatalytic conditions: 1.5 mg/L as the initial concentration of pollutant, 0.61 g/L catalyst, and an irradiation time of 190 min. Further, it was provided that nitrates play a positive role in the removal of this pollutant, while hydrogenocarbonates slow down its elimination. The ecotoxicity evaluation at different trophic levels confirmed the low toxicity of photodegradation by-products. Data analysis demonstrated that response surface methodology is a reliable approach for the optimization of the interactive effects of photocatalytic process parameters and is able to enhance their performance for the complete elimination of this hardly removed water pollutant.

Medicinal Plant Growth in Heavy Metals Contaminated Soils: Responses to Metal Stress and Induced Risks to Human Health.

Accelerating heavy metal pollution is a hot issue due to a continuous growth in consumerism and increased activities in various global industries. Soil contamination with heavy metals has resulted in their incorporation into the human food web via plant components. Accumulation and amplification of heavy metals in human tissues through the consumption of medicinal plants can have hazardous health outcomes. Therefore, in this critical review we aim to bring together published information on this subject, with a special highlight on the knowledge gaps related to heavy metal stress in medicinal plants, their responses, and human health related risks. In this respect, this review outlines the key contamination sources of heavy metals in plants, as well as the absorption, mobilization and translocation of metal ions in plant compartments, while considering their respective mechanisms of detoxification. In addition, this literature review attempts to highlight how stress and defensive strategies operate in plants, pointing out the main stressors, either biotic or abiotic (e.g., heavy metals), and the role of reactive oxygen species (ROS) in stress answers. Finally, in our research, we further aim to capture the risks caused by heavy metals in medicinal plants to human health through the assessment of both a hazard quotient (HQ) and hazard index (HI).

New Evidence of Model Crop Brassica napus L. in Soil Clean-Up: Comparison of Tolerance and Accumulation of Lead and Cadmium.

The potential of the model crop Brassica napus L. (rapeseed) for the phytoremediation of soils polluted with metals was investigated at laboratory scale. The first step consists in the evaluation of the seed germination and growth of the Brassica napus L. plant in a controlled environment, followed by the determination of the photosynthetic pigments content represented by chlorophyll a and b and carotenoids. The degree of metal accumulation in rapeseed has been evaluated by the bioaccumulation factor (BAC), the bioconcentration factor (BCF) and the translocation factor (TF). Phytotoxicity tests were performed in Petri dishes with filter papers moistened with metal solutions in the range of 0 to 300 mg/L Pb(II) or Cd(II). At the highest concentration of the lead and cadmium treatments (300 mg/L), B. napus L. showed the lowest germination degree (56.67% and 43.33%, respectively). According to Tukey test results, Pb(II) concentrations of up to 300 mg/L do not significantly affect the length of the hypocotyls, whereas, in the case of Cd(II), the mean of the radicle and hypocotyl lengths of the seedlings are significantly affected compared to the mean of the control. In soil pot experiments, important changes have been obtained in the pigment content, especially in the case of cadmium. For both metals and for each treatment (100 to 1500 mg/kg Pb(II) and 1 to 30 mg/kg Cd(II)), a TF < 1 indicates an ineffective metal transfer from root to shoot. Finally, rapeseed can be considered a tolerant plant and a suitable candidate for Pb(II) and Cd(II) accumulation and for the phytostabilization of contaminated soil under the experimental conditions adopted in the present study.

Characterization of heavy metal toxicity in some plants and microorganisms-A preliminary approach for environmental bioremediation.

In situ bioremediation processes are important for control of pollution and clean-up of contaminated sites. The study and implementation of such processes can be designed through investigations on natural mechanisms of absorption, biotransformation, bioaccumulation and toxicity of pollutants in plants and microorganisms. Here, the phytotoxic effects of Cr(VI) and Cd(II) on seed germination and plant growth of Lepidium sativum have been examined at various concentrations (30-300 mg/L) in single ion solutions. The studies also addressed the ecotoxicity of metal ions on Azotobacter chroococcum and Pichia sp. isolated from soil. Microbial growth was estimated by weighing the dry biomass and determining the enzymatic activities of dehydrogenase and catalase. The results showed that Cr(VI) and Cd(II) can inhibit L. sativum seed germination and root development, depending on the metal ion and its concentration. The phytotoxic effect of heavy metals was also confirmed by the reduced amounts of dried biomass. Toxicity assays demonstrated the adverse effect of Cr(VI) and Cd(II) on growth of Azotobacter sp. and Pichia sp., manifested by a biomass decrease of more than 50 % at heavy metal concentrations of 150-300 mg/L. The results confirmed close links between phytotoxicity of metals and their bioavailability for phytoextraction. Studies on the bioremediation potential of soils contaminated with Cr(VI) and Cd(II) using microbial strains focusing on Azotobacter sp. and Pichia sp. showed that the microbes can only tolerate heavy metal stress at low concentrations. These investigations on plants and microorganisms revealed their ability to withstand metal toxicity and develop tolerance to heavy metals.

The Effects of a Microorganisms-Based Commercial Product on the Morphological, Biochemical and Yield of Tomato Plants under Two Different Water Regimes.

The practice of organic agriculture represents an essential requirement for conserving natural resources and for providing the food necessary for a growing population, on a sustainable basis. Tomatoes are considered to be one of the most important crops worldwide. In this context, the organic production of tomatoes should be taken into more consideration. The use of microorganisms-based commercial products is an alternative to chemical fertilizers. Anyway, the results of their use are still variable because of various factors. The aim of this study was to test the effect of inoculation with AMF, PGPR and fungi-based products (Rizotech plus®) on the morphological (length of the plants), biochemical (lycopen, polyphenols, antioxidant activity), and number of fruits and yields of four tomato cultivars (Siriana F1, HTP F1, Minaret F1, Inima de Bou) in two different water regimes used for irrigation (200 m3 or 300 m3 of water/hectare) under a protected area. The results showed that the efficiency of Rizotech plus® application is dependent on the cultivar and the amount of water used. Also, it was clearly demonstrated that the microorganism inoculation significantly increased the yield of Minaret F1, Siriana F1 and HTP F1 cultivars as compared to the uninoculated plants, regardless of the water amount used in the experiment. Moreover, it was observed that for the irrigation of all four cultivars, inoculated with Rizotech plus®, a lower amount of water (200 m3·ha-1) can be used to get the same length of plants, number of fruits and yield as in the case of a higher amount of water (300 m3·ha-1). In the case of lycopene, polyphenols and antioxidant activity, the results varied with the cultivar and the water amount used. This study gives new information about the functionality and performance of the microorganisms from Rizotech plus® product when applied to different tomato cultivars grown in a tunnel, in the condition of two different water regimes, contributing to a better characterization of it and maybe to a more efficient use in agriculture to achieve optimum results.

Modelling the behavior of pesticide residues in tomatoes and their associated long-term exposure risks.

This study is focused on the dissipation behavior of 7 fungicides and 5 insecticides applied in tomatoes after a third spraying at recommended and double doses by considering 6 kinetic models which allow estimating the pesticides half-lives (t1/2). Except studying the pesticides dissipation, another scope of our manuscript was investigating the risk to human health after application of different pesticide treatments in tomatoes. The pesticides analysis in tomatoes at harvest showed that the residues were below the maximum residue level (MRL), with the exception of chlorotalonil (included in Group 2B - "Possibly carcinogenic to humans") and bifenthrin for recommended dose treatments, while for double dose treatments, the MRLs was exceeded for 7 pesticides, once again including chlorotalonil. For recommended dose treatments, the 1st order kinetic model is confirmed only for metalaxyl-M. The values of pesticides t1/2 ranged from 0.006 days (for chlorothalonil) to 48.59 days (for myclobutanil). For double dose treatments, the 1st order kinetic model is confirmed for deltamethrin and triadimenol. In this case, the values of pesticides t1/2 ranged from 0.32 to 10.67 days. Further, consumers' exposure was estimated by calculating the long-term risk based on hazard quotient (HQ). The results indicated that the risks generated by pesticide residues in tomatoes applied in recommended or double doses are in an acceptable limit, except for chlorothalonil which may pose a threat for children health. However, if we consider the cumulative hazard index (HI) values which were higher than 1, consumption of tomatoes containing pesticides residues may cause harmful non-carcinogenic health effects.

The role of Arthrobacter viscosus in the removal of Pb(II) from aqueous solutions.

The aim of this paper was to establish the optimum parameters for the biosorption of Pb(II) by dead and living Arthrobacter viscosus biomass from aqueous solution. It was found that at an initial pH of 4 and 26 °C, the dead biomass was able to remove 97% of 100 mg/L Pb(II), while the living biomass removed 96% of 100 mg/L Pb(II) at an initial pH of 6 and 28 ± 2 °C. The results were modeled using various kinetic and isotherm models so as to find out the mechanism of Pb(II) removal by A. viscosus. The modeling results indicated that Pb(II) biosorption by A. viscosus was based on a chemical reaction and that sorption occurred at the functional groups on the surface of the biomass. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX) analyses confirmed these findings. The suitability of living biomass as biosorbent in the form of a biofilm immobilized on star-shaped polyethylene supports was also demonstrated. The results suggest that the use of dead and living A. viscosus for the removal of Pb(II) from aqueous solutions is an effective alternative, considering that up to now it has only been used in the form of biofilms supported on different zeolites.

Rhizobacteria and plant symbiosis in heavy metal uptake and its implications for soil bioremediation.

Certain species of plants can benefit from synergistic effects with plant growth-promoting rhizobacteria (PGPR) that improve plant growth and metal accumulation, mitigating toxic effects on plants and increasing their tolerance to heavy metals. The application of PGPR as biofertilizers and atmospheric nitrogen fixators contributes considerably to the intensification of the phytoremediation process. In this paper, we have built a system consisting of rhizospheric Azotobacter microbial populations and Lepidium sativum plants, growing in solutions containing heavy metals in various concentrations. We examined the ability of the organisms to grow in symbiosis so as to stimulate the plant growth and enhance its tolerance to Cr(VI) and Cd(II), to ultimately provide a reliable phytoremediation system. The study was developed at the laboratory level and, at this stage, does not assess the inherent interactions under real conditions occurring in contaminated fields with autochthonous microflora and under different pedoclimatic conditions and environmental stresses. Azotobacter sp. bacteria could indeed stimulate the average germination efficiency of Lepidium sativum by almost 7%, average root length by 22%, average stem length by 34% and dry biomass by 53%. The growth of L. sativum has been affected to a greater extent in Cd(II) solutions due its higher toxicity compared to that of Cr(VI). The reduced tolerance index (TI, %) indicated that plant growth in symbiosis with PGPR was however affected by heavy metal toxicity, while the tolerance of the plant to heavy metals was enhanced in the bacteria-plant system. A methodology based on artificial neural networks (ANNs) and differential evolution (DE), specifically a neuro-evolutionary approach, was applied to model germination rates, dry biomass and root/stem length and proving the robustness of the experimental data. The errors associated with all four variables are small and the correlation coefficients higher than 0.98, which indicate that the selected models can efficiently predict the experimental data.

Experimental analysis and mathematical prediction of Cd(II) removal by biosorption using support vector machines and genetic algorithms.

We investigated the bioremoval of Cd(II) in batch mode, using dead and living biomass of Trichoderma viride. Kinetic studies revealed three distinct stages of the biosorption process. The pseudo-second order model and the Langmuir model described well the kinetics and equilibrium of the biosorption process, with a determination coefficient, R(2)>0.99. The value of the mean free energy of adsorption, E, is less than 16 kJ/mol at 25 °C, suggesting that, at low temperature, the dominant process involved in Cd(II) biosorption by dead T. viride is the chemical ion-exchange. With the temperature increasing to 40-50 °C, E values are above 16 kJ/mol, showing that the particle diffusion mechanism could play an important role in Cd(II) biosorption. The studies on T. viride growth in Cd(II) solutions and its bioaccumulation performance showed that the living biomass was able to bioaccumulate 100% Cd(II) from a 50 mg/L solution at pH 6.0. The influence of pH, biomass dosage, metal concentration, contact time and temperature on the bioremoval efficiency was evaluated to further assess the biosorption capability of the dead biosorbent. These complex influences were correlated by means of a modeling procedure consisting in data driven approach in which the principles of artificial intelligence were applied with the help of support vector machines (SVM), combined with genetic algorithms (GA). According to our data, the optimal working conditions for the removal of 98.91% Cd(II) by T. viride were found for an aqueous solution containing 26.11 mg/L Cd(II) as follows: pH 6.0, contact time of 3833 min, 8 g/L biosorbent, temperature 46.5 °C. The complete characterization of bioremoval parameters indicates that T. viride is an excellent material to treat wastewater containing low concentrations of metal.