Review and Analysis: Evaluation of the Impacts and Consequences of Using Agricultural Herbicides as Military Chemical Weapons in Second Indochina War

The legacy of the human misery caused by the application of the herbicides including Agent Purple and Agent Orange contaminated with unknown amounts of dioxin TCDD and Agent Blue, the arsenic-based herbicide, sprayed over the jungles, rice fields, and hamlets of Vietnam is still haunting us today. Why did this happen? Could it have been prevented? Was it necessary United States military strategy? Was it an intentional decision to inflict this blight on the enemy soldiers and the Vietnamese, Cambodian, and Laotian civilians, to poison their land and cause generations of harm? Alternatively, was it an unpreventable accident in the march of military history? What patterns in the U.S. government’s thought process could be identified as the cause, which led to the decision to use these herbicides as tactical chemical weapons? If the introduction of herbicide (chemical) weapons had not been made, would the outcome of the Vietnam War and the Secret Wars in Laos and Cambodia have been any different? The objective of this treatise is to outline the role of world events and backgrounds and the role of the leaders, U.S. military, CIA, USDA, U.S. State Department, the U.S. President appointed Ambassadors to Vietnam and Laos, chemical companies, and President Diệm’s Republic of Vietnam (RVN) government and military. Their collective advice led to the decision to use herbicides as military and environmental chemical weapons in the Second Indochina War. Were the National interests achieved by U.S. military strategy in the RVN using herbicide weapons worth the long-term environmental and human health consequences in Vietnam, Cambodia, and Laos? Did it impact the outcome of the Second Indochina War?

Evaluation of Pre-Emergence and Post-Emergence Herbicides for Weed Management in Miscanthus sacchariflorus and Miscanthus sinensis

Miscanthus,is a promising bioenergy crop,considered superior to other bioenergy crops because of its higher water and nutrient use efficiency,cold tolerance,and higher production of biomass.Broadleaf weeds and grass weeds,cause major problems in the Miscanthus field.A field experiment was conducted in 2018 and 2019,to assess the effects of pre-emergence(alachlor and napropamide)and post-emergence herbicides(nicosulfuron,dicamba,bentazon,and glufosinate ammonium)on broadleaf and grass weeds in M.sinensis and M.sacchariflorus fields.The weed control efficiency and phytotoxicity of pre-and post-emergence herbicides were evaluated at 30 days after treatment(DAT)and compared to those of the control plots.The results showed wide variations in the susceptibility of the weed species to the treated herbicides.Treatment with nicosulfuron 40 g.a.i.ha^(-1) provided the most effective overall weed control(with 10%visual injury),without affecting the height and biomass of neither Miscanthus species in the field.Post-emergence herbicides such as glufosinate ammonium 400 g.a.i.ha^(-1) and dicamba 482 g.a.i.ha^(-1) were effective and inhibited the growth and density of the majority of weeds to a 100%;however,they showed significant phytotoxicity(toxicity scale of 1-10)to both species of Miscanthus.The application of glufosinate ammonium caused severe injuries to the foliar region(90%visual injury)of both Miscanthus sps.Comparatively,M.sinensis showed a slightly higher tolerance to the herbicides nicosulfuron,bentazon and napropamide with 10%visual injury at the recommended dose than M.sacchariflorus.The present study clearly showed that infestation of broadleaf and grass weeds in Miscanthus fields can cause significant damage to the growth and biomass of Miscanthus and applying pre-emergence and post-emergence herbicides effectively controls the high infestation of these weeds.

Review and Analysis: Did the United States Transport, Off-Load and Use Commercial 2,4,5-T Herbicides with Unknown Amounts of Dioxin TCDD on Military Base Grounds in Panama Canal Zone between 1948 and 1999?

The 84 km Panama Canal connecting the Atlantic and Pacific oceans has historically been a strategic waterway for shipping and the location of United States (US) military bases. Since the construction of Lake Gatun reservoir, canal locks and navigation channel through the Isthmus of Panama tropical forests in the 1910s, chemicals, pesticides, and herbicides have been essential for controlling upland and wetland vegetation as well as managing mosquito-borne diseases. Chemicals and pesticides flowed into Lake Gatun via land surface runoff and subsurface drainage either attached to the sediment or in solution during the rainy season. Lake Gatun and the Panama Canal was the drinking water source for most of the civilian and military population living in the Panama Canal Zone. Between 1948 and 1999, US military base commanders had the ability to order, from the Federal Supply Catalog, commercially available herbicide 2,4,5-T with unknown amounts of dioxin TCDD for use on the military base grounds in the Panama Canal Zone. The herbicide 2,4,5-T was transported to Panama Canal Zone ports, including the ports Cristobal on the Caribbean and Balboa on the Pacific, and distributed to the US military bases in Panama by rail or truck. The US National Toxicology Program and the International Agency for the Research on Cancer listed dioxin and TCDD as known human carcinogens. Dioxins are endocrine disrupters and can cause certain chloracne, cancers, developmental and reproductive effects. In 1985, the United States government banned the manufacture of the herbicide 2,4,5-T, with unknown amounts of dioxin TCDD, after it was shown to cause cancer in animals. The objectives of this study are to determine: 1) the fate of dioxin TCDD, a contaminant in the herbicide 2,4,5-T, sprayed on the US military base vegetation in the Panama Canal Zone from 1948 to 1999, 2) the transport of dioxin TCDD rich sediment via soil erosion and overland flow into Lake Gatun and Panama Canal waterways and 3) the human health impacts of dioxin TCDD, a known carcinogen, on US military and Panamanian civilians exposed to dioxin TCDD in the Panama Canal Zone.

A nonsynonymous mutation in an acetolactate synthase gene (Gh_D10G1253) is required for tolerance to imidazolinone herbicides in cotton

Background Herbicide tolerance in crops enables them to survive when lethal doses of herbicides are applied to surrounding weeds.Herbicide-tolerant crops can be developed through transgenic approaches or traditional mutagenesis approaches.At present,no transgenic herbicide tolerant cotton have been commercialized in China due to the genetically-modified organism(GMO)regulation law.We aim to develop a non-transgenic herbicide-tolerant cotton through ethyl methanesulfonate(EMS)mutagenesis,offering an alternative choice for weed management.Results Seeds of an elite cotton cultivar Lumianyan 37(Lu37)were treated with EMS,and a mutant Lu37-1 showed strong tolerance to imidazolinone(IMI)herbicides was identified.A novel nonsynonymous substitution mutation Ser642Asn at acetolactate synthase(ALS)(Gh_D10G1253)in Lu37-1 mutant line was found to be the potential cause to the IMI herbicides tolerance in cotton.The Ser642Asn mutation in ALS did not present among the genomes of natural Gossypium species.Cleaved amplified polymorphic sequence(CAPS)markers were developed to identify the ALS mutant allele.The Arabidopsis overexpressing the mutanted ALS also showed high tolerance to IMI herbicides.Conclusion The nonsynonymous substitution mutation Ser642Asn of the ALS gene Gh_D10G1253 is a novel identi-fied mutation in cotton.This substitution mutation has also been identified in the orthologous ALS genes in other crops.This mutant ALS allele can be used to develop IMI herbicide-tolerant crops via a non-transgenic or transgenic approach.

Effects of Different Herbicides on Weed Control in Alfalfa Field

[Objectives]The paper was to systematically study the technology of weed control in alfalfa field.[Methods]Reviving alfalfa field and newly sown alfalfa field after emergence were selected,and the effects of different herbicides on weed control and alfalfa yield were discussed.[Results]The optimal herbicides after alfalfa reviving were 5%imazethapyr and 10%imazethapyr,and the optimal dosages were 1.5 and 1.05 L/hm 2,respectively.The optimal herbicides after emergence of newly born alfalfa were 5%imazethapyr and 10%imazethapyr,and the optimal dosages were 1.5 and 0.75 L/hm 2,respectively.[Conclusions]This study will provide a technical support for high quality production of alfalfa.

Limiting Factors and Countermeasures for the Development of Biological Herbicides

This paper mainly analyzes the main limiting factors in the development of biological herbicides,such as narrow herbicidal spectrum,vulnerable to environmental impacts,difficulties in preparing dosage forms,difficult separation and low yield of active substances,biological safety,etc.Moreover,countermeasures and suggestions are put forward,including strengthening the study of biological screening of herbicidal activity,microbial metabolites and their use as lead compounds,dosage forms,fungi complex formulation,fungi and herbicide complex formulation,and fermentation technology.

Evaluation of Commercial Active Carbons for the Removal of s-Triazine Herbicides from Waters

The adsorption capacity of powdered active carbons, used in a water treatment facility, for the removal of the triazine herbicides propazine, prometryn and prometon, was evaluated. Kinetic studies showed that some of the carbon samples used could be suitable in the practice for the treatment of moderate contents of the herbicides in contaminated waters. Equilibrium studies showed that the data fit the Frumkin isotherm. The results show that in the adsorption process there are repulsive lateral interactions that depend mainly of the adsorbate molecules rather than the nature or distribution of adsorption sites. Such lateral interactions seem to be established mainly between the isopropyl groups of adjacent molecules, being of the same order for the three molecules. The effectiveness of the active carbons was evaluated by determining the percentage of reduction achieved by each product.

Effect of Two Herbicides on the Growth of Early Seedlings of Rye(Secale cereale)

[Objective]The aim was to study the effect of herbicide on the growth of early seedlings of rye（Secale cereale）.[Method]Effect of two kinds of herbicide（Atrazine and APM）on seedling growth of rye was investigated at the physiological,biochemical and cellular level.[Result]The Atrazin significantly decreased the contents of chlorophyll a,b and soluble proteins.Rye seeds were treated with 0.01-1 mg/L Atrazine for 16 h,the contents of chlorophyll a and b decreased from 1.26（a）,0.49（b）mg/g FW（control）to 1.15（a）,0.46（b）mg/g FW（0.1 mg/L）and 0.81（a）,0.33（b）mg/g FW（1.0 mg/L）.The content of soluble protein decreased with the increasing concentration of Atrazin.Atrazin had no significant influence on the cell division and chromosome structure variation.The contents of chlorophyll a,b and soluble proteins had no significantly change under the treatment of APM,but the number of chromosome structure variation such as chromosome bridge,multipolar division cells,lagging chromosome and unequal division cells increased significantly.[Conclusion]The critical concentration of Atrazine was 0.1-1.0 mg/L and 4 mg/L of APM in rye.

Research Status of Amide Herbicides and Their Safeners

The widespread use of chemical herbicides especially amide herbicides has promoted the innovation of chemical weeding in farmland, but amide herbicides have brought invisible chemical injuries to crops in addition to weeding. Herbi-cidesafeners should be applied at the same time with herbicides to ensure herbi- cides will not injure crops while controlling weeds. The research and application of safeners is of great significance to resolving or alleviating the negative effects of herbicides on crop growth. The overview, mechanism, applied research progress and existing problems of amide herbicides and their safenars are summarized.

Glyphosate-Resistant Giant Ragweed(Ambrosia trifida L.):2,4-D Dose Response and Control with Postemergence Herbicides in Soybean

Glyphosate resistant giant ragweed is an increasing problem in glyphosate resistant cropping systems in southwestern Ontario. The postemergence herbicides registered for use in soybean in Ontario do not provide consistent control of glyphosate resistant giant ragweed. There is limited research on the lowest effective rate of 2,4-D for the control of glyphosate resistant giant ragweed. Consequently, the objectives of this study were a) to determine the efficacy of herbicides applied postemergence for the control of glyphosate resistant giant ragweed in glyphosate resistant soybean, and b) to determine the lowest effective rate of 2,4-D for the control of glyphosate-resistant giant ragweed. Ten postemergence herbicide combinations and seven rates of 2,4-D were evaluated in field studies conducted in 2011 and 2012 at six locations confirmed with glyphosate-resistant giant ragweed. The post emergence herbicides evaluated did not provide acceptable/consistent control. Of the herbicides evaluated, glyphosate plus cloransulam-methyl provided 26% to 70% control 8 WAA of glyphosate resistant giant ragweed, which was the best of the herbicides combinations evaluated. The doses of 2,4-D required to reduce giant ragweed shoot dry weight by 50, 80 and 95% were 142, 310 and 1048 g a.e. ha-1, respectively.

Phytotoxicity of four herbicides on Ceratophyllum demersum,Vallisneria natans and Elodea nuttallii

The physiological effects of 4 herbicides （butachlor, quinclorac, bensulfuron-methyl and atrazine） on 3 submerged macrophytes （Ceratophyllum demersum, Vallisneria natans and Elodea nuttallii） were tested in laboratory. The variables of the relative growth rate and the photosynthetic pigment content showed that all of the tested herbicides affected the growth of the plants obviously, even at the lowest concentration （0.0001 mg/L）. Except for the C. demersum treated with quinclorac at 0.005 and 0.01 mg/L, the relative growth rates of the plants were inhibited significantly （p 〈 0.01）. Statistical analysis of chlorophyll a （Chl-a） contents was carded out with both the t-test and one-way ANOVA to determine the difference between the treatment and control. The results showed that Chl-a contents of the plants in all treatment groups were affected by herbicides significantly, except for the C. demersum treated with bensulfuron-methyl at 0.0005 mg/L. The decrease in Chl-a content was positively correlated to the dosage of the herbicides in most treatment groups. It was suggested that herbicides in water bodies might potentially affect the growth of aquatic macrophytes. Since the Chl-a content of submerged macrophytes responded to the stress of herbicides sensitively and directly, it could be used as a biomaker in environmental monitoring or in the ecological risk assessment of herbicide contamination.

Adsorption of chloroacetanilide herbicides on soil and its components III. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca 2+ \|, Mg 2+ \|, Al 3+ \| and Fe 3+ \| saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, K f decreased in the order of metolachlor > acetolachlor > alachlor > propachlor on the same clay. FT IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg 2+ <Ca 2+ <Al 3+ ≤Fe 3+ which coincided with the increasing acidity of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay to humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.

Glutathione-Responsive Carboxymethyl Chitosan Nanoparticles for Controlled Release of Herbicides

Glutathione-responsive carboxymethyl chitosan nanoparticles cross-linked with disulfide bonds were developed for controlled release of herbicides. The nanoparticles were synthesized by selfassembly of amphiphilic carboxymethyl chitosan derivative (CMCS-MUA) in aqueous solution and subsequently producing disulfide cross-linking bonds by ultrasonic treatment. TEM showed that the nanoparticles had a spherical core-shell configuration with a size of about 250 nm. Assessment of stability of the nanoparticles (considering mean diameter, polydispersity, and Zeta potential) was conducted over a period of three months, and the nanoparticles were found to be stable in solution. Herbicide-loaded nanoparticles were prepared using diuron as a model herbicide. In vitro release study revealed that diuron can be released from nanoparticles in a controlled manner depended on the glutathione concentration. Herbicidal activity assays performed with preemergence treatment of target species (Echinochloa crusgalli) showed the effectiveness of diuron- loaded nanoparticles. Assays with nontarget species (Zea mays) showed that the diuronloaded nanoparticles did not affect plant growth. The results indicate that the glutathioneresponsive nanoparticles prepared in this work will be a promising candidate for controlled release of herbicides in agriculture.

Integrated Weed Management Through Tillage and Herbicides for Wheat Production in Rice-Wheat Cropping System in Northwestern Pakistan

Conservational tillage （CT） in combination with broad spectrum herbicide may be more efficient and economical in controlling weeds, reducing cost of cultivation, and enhancing wheat yield. Field experiments were carried out to evaluate the effect of tillage and herbicides on weeds and wheat yield under rice-wheat cropping system （RWCS）. The results indicated that broad spectrum herbicides particularly, carfentrazone ethyl ester＋ isoproturon （Affinity 50 WDG） reduced weeds density by 93 and 95% compared to control and also produced the maximum grain yield （6 818 and 6 996 kg ha-l） and HI （harvest index, 44.7 and 44.6%） in 2007-2008 and 2008-2009 growing seasons, respectively. The maximum weeds infestation and the lowest yield were recorded in control. Tillage methods significantly influenced grain yield and HI, while no significant effect on all other parameters. The overall mean yield was significantly higher in zero tillage （5 575 kg ha-l） and reduced tillage （5 584 kg ha-l） compared to CT （5 479 kg ha-^-1）. Besides increasing wheat yield, Affinity 50 WDG and zero tillage are important weed management practices that can be integrated into wheat production in RWCS. However, in case of perennial weeds or insect pests＇ infestation, CT in combination with Affinity 50 WDG would be more productive than conservation tillage.

Effects of Four Kinds of Triazine Herbicides on the Photoquenching Degradation of Acetochlor

Effects of four kinds of triazine herbicides on the photodegradation of acetochlor were studied on glass surface and in aqueous solution under three kinds of light sources, i.e., xenon lamp, high pressure mercury lamp and natural sunlight. The results indicated that atrazine, simetryne, prometryne and ametryne exhibited significant effects on the photoquenching degradation of acetochlor, and there was an obvious positive correlation between their effects and the dosage of four kinds of triazine herbicides.

Effects of Different Herbicides on Maize Growth and Weed Control in Maize Fields

Effects of four herbicides(paraquat, acetochlor, nicosulfuron and atrazine) on the growth of maize and control effect of plant quantity and fresh weight of weeds were studied. The results showed that 15 days after spraying the herbicides on weeds,the prevention and control effect of paraquat on weeds was the optimum, and its effects on the plant quantity and fresh weight of weeds were above 81.57%; the prevention and control effect of acetochlor on weeds was the second best; the prevention and control effect of atrazine on weeds was the worst, and its effects on the plant quantity and fresh weight of weeds were only 51.04% and 37.86%. After 30 or 45 days, the prevention and control effect of atrazine and nicosulfuron on weeds in the maize fields was better than the other herbicides, and their effects on the plant quantity and fresh weight of weeds were higher than 70.00% and 85.00%. Acetochlor and paraquat had certain phytotoxicity to the growth of maize after about 15 days, and its leaves became yellow and grew slowly. On the whole, nicosulfuron had good prevention and control effect on weeds and had no phytotoxicity to the growth of maize.

Control of Glyphosate and Acetolactate Synthase Resistant Common Ragweed (Ambrosia artemisiifolia L.) in Soybean (Glycine max L.) with Preplant Herbicides

A population of common ragweed in Ontario was confirmed to be resistant to glyphosate in 2011. Group 2 [acetolactate synthase (ALS) inhibitors] resistant common ragweed was first confirmed in Ontario in 2000. Previously, glyphosate provided excellent control of common ragweed in glyphosate resistant soybean but with the confirmation of glyphosate resistant (GR) common ragweed, alternative herbicides need to be evaluated. Eight field trials with preplant herbicides were completed over two years (2013 and 2014) in fields with confirmed GR common ragweed. Tank-mixes of glyphosate and linuron or metribuzin provided 88% - 99% and 86% - 98% control 4 weeks after application (WAA) and 80% - 92% and 80% - 95% control 8 WAA, respectively. However, these herbicides also had among the highest environmental impact of the herbicides tested. Based on the results of these studies, GR common ragweed can be controlled with residual herbicides when applied preemergence in soybean. Currently, there are no post emergence herbicides that provide adequate control of GR common ragweed, therefore, preemergence herbicides with residual are essential for full season control.

Rapid Residue Analysis of Sulfonylurea Herbicides in Surface Water: Methodology and Residue Findings in eastern Tiaoxi River of China

A new method combining QuEChERS (quick, easy, cheap, effective, rugged and safe) and DLLME (dispersive liquid–liquid microextraction) for the simultaneous determination of residues of ten sulfonylurea herbicide in water using UPLC-MS/MS was developed and validated. Analytes were extracted and purified with QuEChERS and concentrated in chlorobenzene by applying the DLLME procedure. Several extraction parameters were tested, such as volume, extractive solvent by the QuEChERS method and subsequently used for DLLME, selection of extractive solvent and its volume, was tested. The developed method was validated on the basis of international guidelines. Mean recoveries ranged from 81.2 to 104.9%. Repeatability and reproducibility were lower than 10%. Limits of detection (LODs) and quantification (LOQs) were below 0.074 μg/L and 0.244 μg/L, respectively. Decision limit (CCα) and detection capability (CCβ) were calculated and CCβ ranged from 0.101 μg/L (pyrazosulfuron-ethyl) to 0.260 μg/L (nicosulfuron). Finally, when the method was applied to real samples, traces of three compounds were found in 42 samples and only thifensulfuon-methyl was detected above the LOQ in three samples at 0.17-0.20 μg/L.

Assessment of Triazine Herbicides in Soil by Microwave-assisted Extraction Followed by Gas Chromatography Coupled to Mass Spectrometry Detection

An alternative and fast method for the analysis of a mixture of nine triazines herbicides in soil is presented. The method is based on MAE （microwave-assisted extraction） of herbicides using ethyl acetate as extractant. The economy in the use of solvents coupled with the decrease in extraction time and lower power consumption make MAE a technique that meets the principles of green chemistry. MAE operational parameters, extraction time, mass of the sample and extraction temperature, were optimized by RSM （response surface methodology）. Determination of analytes was completed using gas chromatograph coupled to mass spectrometry detection. The selected triazines could be efficiently extracted by the solvent at 80 ℃ for 10 min, with 80% output of maximum power. When the optimized method was applied to analysis samples, the recoveries of analytes ranged from 81.8 to 106.0% and relative standard deviations were lower than 8.41%. The method is stable and reasonable, which can be used for the determination of ninetriazine herbicides residues in soil.

Investigations on the Degradation of Triazine Herbicides in Water by Photo-Fenton Process

In this work, the degradation of 2-chloro-4,6-diamino-1,3,5-triazine in aqueous solutions by photo-Fenton process has been investigated. The preliminary results have shown that the degradation of 2-chloro-4,6-diamino-1,3,5-triazine by photo-Fenton process is more rapid and more effective than Fenton and UV/H2O2 processes. The effects of certain experimental parameters on kinetics and efficiency of the degradation of 2-chloro-4,6,-diamino-1,3,5-triazine by photo-Fenton process, have been evaluated. Under optimal conditions, photo-Fenton process achieved more than 90% of chloride release and about 30% of nitrate formation. The results of total organic carbon (TOC) and total Kjeldahl nitrogen (TKN) analyses have shown that no carbon dioxide and ammonia are formed during photo-Fenton treatment of aqueous solutions containing 40 mg/L triazine. These results indicate that only substituent groups of triazine ring are released;however, nitrogen atoms of triazine ring remain unaffected. A simple mechanism of degradation of 2-chloro-4,6-diamino-1,3,5-triazine has been proposed. The degradation starts by a rapid release of chlorine atoms as chloride ions to form 2-hydroxy-4,6-diamino-1,3,5-triazine. The amino groups of 2-hydroxy-4,6-diamino-1,3,5-triazine undergo are oxidized into nitro groups by hydroxyl radicals to form 2-hydroxy-4,6-dinitro-1,3,5-triazine which undergoes a slow release of nitro groups and their substitution with hydroxyl groups to form cyanuric acid and nitrate ions. The degradation of cyanuric acid by photo-Fenton process has also been investigated. The results of TOC and TKN analyzes show that no carbon dioxide is formed during the treatment.