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?

Control Effects of 3 Kinds of Herbicides against Weeds in Dogbane (Apocynum venetum) Field

[ Objective] The paper was to explore the control effects of 3 kinds of herbicides against weeds in dogbane （Apocynum venetum） field. [ Method ] Using haloxyfop-R-mithyl and quizalofop-ethyl EC specifically killing monagenns gramineous weeds and chipton specifically killing dicotyledonous broad-leaf weeds, the control test against weeds in 2-year-old dogbane field was carried out. [ Result ] Haloxyfop-R-mithyl had good control effect against gramincous weeds, and its control effect against both barnyard weed （ Echinochloa crusgalli） and green bristleweed （ Setaria viridis ） was greater than 35.0% ; the control effects of quizalofop- ethyl EC against barnyard weed and green bristleweed were 14.8% and 28.6%, respectively; chipt0n had good control effect against Chenopodium album, and the control effect reached 30.8%. Moreover, 3 herbicides did not cause damage to dogbane. [ Conclusion] The study provide theoretical basis for completing cultivation technique of dogbane.

Control Effect Evaluation of Herbicides for Malignant Weed Nut Grass in Sugarcane Field

In order to screen herbicides with ideal safety characteristics to control malignant weed nut grass in sugarcane field, 20% thifensulfuron methyl WP and 65% MCPA·ametryne·diuron WP were selected for the field efficacy trial. The results showed that 20% thifensulfuron methyl WP and 65% MCPA·ametryne·diuron WP had good control effect on nut grass. The optimum dosage of 20% thifensulfuron methyl WP and 65% MCPA.ametryne-diuron WP was 1 125 g/hm^2 （effective ingredients 225 g） and 3 150 g/hm^2 （effective ingredients 2 047.5 g）, respectively. These two herbicides should be dissolved in 675 kg water per hectare and applied in the vigorous growth period of nut grass （height 10-15 cm） with oriented stem leaf spraying. The control effect after 15 days could be above 87.9%.

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.

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.

Inheritance and molecular characterization of resistance to AHAS- inhibiting herbicides in rapeseed

Rapeseed is a very important oil crop in China; however, its production is challenging due to the absence of effective weed management strategies. This is predominantly because of a shortage of herbicide resistance genes. Acetohydroxyacid synthase （AHAS） herbicides inhibit AHAS, a key enzyme involved in branched-chain amino acid synthesis that is required for plant growth. A rapeseed line designated M342 with AHAS herbicide resistance was developed through seed muta- genesis and was studied to assess the level and mode of inheritance of the resistance and to identify the molecular basis of resistance. M342 possessed a high level of cross-resistance to sulfonylureas （SUs） and imidazolinones （IMIs）. This resistance was due to AHAS insensitivity to these herbicides and was inherited as a dominant trait conferred by a single nuclear-encoded gene. Molecular analysis revealed the presence of a Trp574Leu mutation in M342, and an allele-specific cleaved amplified polymorphic sequence （AS-CAPS） marker was developed and cosegregated with herbicide resistance in the F2, BC1, and BC2 populations. This mutation altered the transcript levels of BnAHAS1 and BnAHAS3 in M342 compared with those in the wild type, but it did not affect the agronomic or quality traits. The simple genetic inheritance of this mutation and the availability of the cleaved amplified polymorphic sequence （CAPS） marker and herbicide resistance gene should facilitate the development of herbicide-resistant rapeseed cultivars for effective weed control in China.

Effect of Cadmium and Herbicides on the Growth, Chlorophyll and Soluble Sugar Content in Rice Seedlings

To investigate the combined effects of Cd^2＋ （ 0,10,100,500 μmol/L） , acetochlor （AC） （0,1.6,4.0,8.0μmol/L）, and bensulfuronmethyl （BSM） （ 0,0.16,0.40,0.80 μmol/L） on the biomass,leaf soluble sugar, total chlorophyll （chl） content, chl a/b ratio, and Cd content in roots and shoots in the rice seedlings, pot culture experiments were conducted with rice （Oryza sativa L. ） cultivar Jinyou 402. The results showed that the Cd and AC combined treatment （Cd＋ AC treatment） significantly inhibited the growth of the roots and shoots. The root dry weight/shoot dry weight （RDW/SDW） ratio, total chlorophyll content and chl a/b ratio decreased by 41%, 50%, 56% , respectively, in comparison with the control, as well as the leaf soluble sugar content, plant dry weight /plant fresh weight （PDW/PFW） ratio increased by 284% and 44% , respectively. Cd content in the roots and shoots had a decreasing tendency with the increasing concentration of AC under the Cd＋AC treatment. The Cd and BSM combined treatment （Cd＋BSM treatment） had a similar result to the Cd＋AC treatment. The results suggest that the toxicity of Cd to rice seedlings has been enhanced due to its combination with herbicides.

Predicting herbicides concentrations in paddy water and runoff to the river basin

This study was conducted to investigate the dissipation pattern and runoff of herbicides to the river basin from the paddy fields. Pesticide paddy field model(PADDY) was applied to predict herbicide concentration in paddy fields. A field study was conducted in a paddy farm of Higashi Hiroshima City, Hiroshima Prefecture, Japan in the year of 2003 paddy season. The herbicides were mefenacet, thiobencarb, and bensulfuron methyl. The sample water was analyzed by using gas chromatography and HPLC after solid phase extraction. Predicted dissipation rate of thiobencarb in paddy water was higher(DT_ 50 = 4 36) than that measured, with a lower k value(-0 069). Two weeks after application no thiobencarb was detected in the drainage channel and down stream. In the down stream, thiobencarb was detected until 3 d after application, with a range of 0 02% to 0 08% of applied herbicide. The predicted dissipation rate(k) and half-life(DT_ 50 ) of mefenacet was not significantly different from that of measured. In the drainage channel, upstream and downstream mefenacet was found during the whole study period. In downstream, the maximum concentration of mefenacet was present 0 61% of applied in the paddy field on 3DAH. The dissipation rate(k) of BSM varied from -0 0860 to -0 1059 to with half-life(DT_ 50 ) 3 5 and 2 84 d. In upstream water, no BSM was detected except trace amounts(0 01 μg/L) at 3 d after application. However, in the drainage channel 8%, 6% and 1 58% of applied BSM was present at 0, 1 and 3 d after application respectively. In the down stream, the highest concentration was 1 06%, shortly after application.

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 and correlation with their thermodynamic properties of triazine herbicides on soils

Adsorption of atrazine, prometryne and prometon was determined on six soils with different physical and chemical properties. The adsorption isotherms of three herbicides could well fit Freundlich equation. On all of six soils, adsorption of herbicides increased in the order: atrazine ≈prometon<prometryne. This order is quite the same to the calculation result of by means of excess thermodynamic properties of triazine. The Freundlich adsorption constants, K f, showed to have good correlation with organic matter(OM%) of soils for each of these herbicides, suggesting that OM is the main factor, which dominates in the adsorption process of these triazine herbicides.

Trp_(548)Met mutation of acetolactate synthase in rice confers resistance to a broad spectrum of ALS-inhibiting herbicides

Herbicide resistance in crop plants is valuable for integrated weed management in agriculture. Herbicide resistant rice, in particular, is important to management of weedy rice, a close relative of cultivated rice and a noxious weed prevalent in rice fields that remains challenging to farmers worldwide. Herbicide resistant plants can be obtained through transgenic approach or by mutagenesis of regular plant and screening of mutants with elevated resistance to herbicide. In this study, we conducted ethyl methyl sulfonate mutagenesis(EMS) to elite indica cultivar Huanghuazhan(HHZ) and screened for mutants resistant to imazapic, a herbicide that can inhibit the acetolactate synthase(ALS) in plants. We obtained three mutants of Os ALS gene that have not been reported previously in rice. One of the mutants, with Trp_(548) changed to Met(W_(548)M), was analyzed in more details in this study. This mutation had no negative effect on the plant physiology and morphology as well as rice yield. Compared with the imidazolinone-resistant mutant S_(627)N(Ser_(627) changed to Asn) that has been deployed for Clearfield rice development, W_(548)M mutant showed high levels of resistance to a broad spectrum of five families of ALSinhibiting herbicides, in addition to a higher level of resistance to herbicides of the imidazolinone family.The herbicide-resistance was stably inherited by crossing into other rice lines. Thus, the W_(548)M mutation provides a valuable resource for breeding of herbicide resistant rice and weed management.

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.

Simultaneous Voltammetric Determination of Three Herbicides in Food and Water Samples with the Aid of Chemometrics

Differential pulse stripping voltammetry method（DPSV） was applied to the determination of three herbicides, ametryn, cyanatryn, and dimethametryn. It was found that their voltammograms overlapped strongly, and it is difficult to determine these compounds individually from their mixtures. With the aid of chemometrics, classical least squares（CLS）, principal component regression（PCR） and partial least squares（PLS）, voltammogram resolution and quantitative analysis of the synthetic mixtures of the three compounds were successfully performed. The proposed method was also applied to the analysis of some real samples with satisfactory results.

Effect of Starch Sources on the Release Rates of Herbicides Encapsulated

The effects of starch sources on the behaviors of starch matrices and on the rates of herbicides released from the matrices were studied for slow release. The starches considered include native corn starch, wheat starch, potato starch and cassava starch. The matrices were prepared through encapsulating 2,4-dichlorophenoxyacetic or 2,4,5 trichlorophenoxyacetic acids as model herbicides with hot-gelatinized starch pastes. The encapsulation was evaluated in terms of herbicide content, swellability, encapsulation efficiency, and release rate. The results show that starch sources play an important role on the matrix behaviors and on release rates. The rate of 2,4-D released follows the order： wheat starch 〈 potaot starch 〈 corn starch 〈 cassava starch. And for the rate of 2,4,5-T, this order is nearly the same only with an exception that the late two kinds of starch are similar. It is also demonstrated that herbicides with different water solubility show different release rates, no matter what type of starch is used as the matrices.

Degradation of Herbicides Atrazine and Bentazone Applied Alone and in Combination in Soils

The application of a mixture of bentazone(3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide)and atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine)is a practical approach to enhance the herbicidal effect.Labo- ratory incubation experiments were performed to study the degradation of bentazone and atrazine applied in combination and individually in maize rhizosphere and non-rhizosphere soils.After a lag phase,the degradation of each individual herbicide in the non-autoclaved soil could be adequately described using a first-order kinetic equation.During a 30-d in- cubation,in the autoclaved rhizosphere soil,bentazone and atrazine did not noticeably degrade,but in the non-autoclaved soil,they rapidly degraded in both non-rhizosphere and rhizosphere soils with half-lives of 19.9 and 20.2 d for bentazone and 29.1 and 25.7 d for atrazine,respectively.The rhizosphere effect significantly enhanced the degradation of atrazine, but had no significant effect on bentazone.These results indicated that biological degradation accounted for the degrada- tion of both herbicides in the soil.When compared with the degradation of the herbicide applied alone,the degradation rates of the herbicides applied in combination in the soils were lower and the lag phase increased.With the addition of a surfactant,Tween-20,a reduced lag phase of degradation was observed for both herbicides applied in combination. The degradation rate of bentazone accelerated,whereas that of atrazine remained nearly unchanged.Thus,when these two herbicides were used simultaneously,their persistence in the soil was generally prolonged,and the environmental contamination potential increased.

Adsorption of Acetanilide Herbicides on Soil and Its Components: Ⅳ. Sorption of Acetanilide Herbicides on Soils and its Correlation with Soil Properties

Sorption of acetanilide herbicides, metolachlor, acetochlor, pretilachlor and butachlor on eight soils with various physical and chemical properties was studied. The adsorption isotherms could fit Freundich equation well (r 2 ≥0.91) and the adsorption extents increased in the order: metolachlor < acetochlor < pratilachlor < butachlor. The product of Freundlich adsorption constants, Kf (1/n), showed to have a good correlation with organic matter content (OM) of soils for each of these herbicides, suggesting that OM is the primary factor dominating in the adsorption process of these asetanilide herbicides. Multivariant correlation regression between Kf (1/n) and two factors, water solubility (S.) of herbicides and OM, was also performed. Kf(1/n) correlated with 1/S. and OM/S. well, showing that high S. corresponds to a weak tendency to adsorb on soils. Infrared (IR) spectra and electron spin resonance (ESR) parameters confirmed that multifunctional H-bonds and charge-transfer bonds were the main adsorption mechanisms of these acetanilide herbicides. The abilities of herbicides to form these adsorption bonds with HA increased in the same order as the extent of adsorption.

Metsulfuron-methyl Molecularly Imprinted Stir Bar Sorptive Extraction Coupled with High Performance Liquid Chromatography for Trace Sulfonylurea Herbicides Analysis in Complex Samples

Metsulfuron-methyl molecularly imprinted polymer（MIP）-coated stir bar was prepared for sorptive extraction of sulfonylurea herbicides in complex samples.The MIP-coating was about 21.3 μm thickness with the relative standard deviation（RSD） of 4.4%（n=10）.It was homogeneous and porous with good thermal stability and chemical stability.The extraction capability of the MIP-coating was 2.8 times over that of the non-imprinted polymer（NIP）-coating in hexane.The MIP-coating exhibited selective adsorption ability to the template and its analogues.The extraction conditions,including extraction solvent,desorption solvent,extraction time,desorption time and stirring speed,were optimized.A method for the determination of six sulfonylurea herbicides by MIP-coated stir bar sorptive extraction coupled with high performance liquid chromatography（HPLC） was developed.The linear range was 10―200 μg/L and the detection limits were within a range of 2.0―3.3 μg/L.It was also applied to the analysis of sulfonylurea herbicides in spiked river water,soil and rice samples.

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.

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.