Knowledge, attitudes and practices to reduce exposure among residents living near Danang dioxin hot spot : 2.5 years after a preventative intervention

Da Nang Airbase in Viet Nam served as a bulk storage and supply facility for Agent Orange and other herbicides during Operation Ranch Hand 1961-1971[1]. Studies have shown that environmental and biological samples taken around the airbase site have elevated levels of dioxin [1-3]. Residents living in the vicinity of the airbase are at risk of exposure to dioxin in soil, water and mud and particularly through the consumption of local contaminated food. In 2009, a pre-intervention cross sectional survey was undertaken. This survey examined the knowledge, attitudes and practices (KAP) of householders living near Da Nang Airbase, relevent to reducing dioxin exposure through contaminated food. The results showed that despite living near a severe dioxin hot spot, the residents had very limited knowledge of both exposure risk and measures to reduce exposure to dioxin[4]. In response, the Vietnam Public Health Association (VPHA) and Da Nang Public Health Association implemented a risk reduction program at four residential wards in the vicinities of the Da Nang Airbase in 2010. A post intervention KAP survey was under taken in 2011, and the results showed that knowledge of the existence of dioxin in food, dioxin exposure pathways, potential high risk foods, and preventive measures was significantly enhanced. This new study monitored KAP 2.5 years after the intervention through a 2013 survey of food handlers from 400 households that were randomly selected from the four intervention wards. The results show that most of the positive outcomes remained stable or had increased; some KAP indicators decreased compared to those in the post-intervention survey, but were still significantly higher than the pre-intervention levels. In 2014, these findings will be incorporated with qualitative assessments and the results of laboratory analysis of dioxin concentrations in foods in Da Nang and Bien Hoa dioxin hot spots to comprehensively assess the sustained effects of the intervention.

Hydrolysis of triasulfuron, metsulfuron-methyl and chlorsulfuron in alkaline soil and aqueous solutions

The hydrolysis of triasulfuron, metsulfuron-methyl and chlorsulfuron in aqueous buffer solutions and in soil suspensions at pH values ranging from 5.2 to 11.2 was investigated. Hydrolysis of all three compounds in both aqueous buffer and soil suspensions was highly pH-sensitive. The rate of hydrolysis was much faster in the acidic pH range (5.2-6.2) than under neutral and moderately alkaline conditions (8.2-9.4), but it increased rapidly as the pH exceeded 10.2. All three compounds degraded faster at pH 5.2 than at pH 11.2. Hydrolysis rates of all three compounds could be described well with pseudo-first-order kinetics. There were no significant differences (P =0.05) in the rate constants (k, day-1) of the three compounds in soil suspensions from those in buffer solutions within the pH ranges studied. A functional relationship based on the propensity of nonionic and anionic species of the herbicides to hydrolyse was used to describe the dependence of the 'rate constant' on pH. The hydrolysis involving attack by neutral water was at least 100-fold faster when the sulfonylurea herbicides were undissociated (acidic conditions) than when they were present as the anion at near neutral pH. In aqueous buffer solution at pH > 11, a prominent degradation pathway involved O-demethylation of metsulfuron-methyl to yield a highly polar degradate, and hydrolytic opening of the triazine ring. It is concluded that these herbicides are not likely to degrade substantially through hydrolysis in most agricultural (C) 2000 Society of Chemical Industry.

Crystal structures and hydrogen bonding in the anhydrous tryptaminium salts of the isomeric (2,4-dichlorophenoxy)acetic and (3,5-dichlorophenoxy)acetic acids

The anhydrous salts of 1H-indole-3-ethanamine (tryptamine) with isomeric (2,4-dichlorophenoxy)acetic acid (2,4-D) and (3,5-dichlorophenoxy)acetic (3,5-D), C10H13N2+ (C8H5Cl2O3)-, [(I) and (II), respectively] have been determined and their one-dimensional hydrogen-bonded polymeric structures are described. In the crystal of (I),the aminium H-atoms are involved in three separate inter-species N-H...O hydrogen-bonding interactions, two with carboxyl O-atom acceptors and the third in an asymmetric three-centre bidentate carboxyl O,O' chelate [graph set R2/1(4)]. The indole H-atom forms an N-H...O~carboxyl~ hydrogen bond, extending the chain structure along the b axial direction. In (II), two of the three aminium H-atoms are also involved in N-H...O(carboxyl) hydrogen bonds similar to (I) but with the third, a three-centre asymmetric interaction with carboxyl and phenoxy O-atoms is found [graph set R2/1(5)]. The chain polymeric extension is also along b. There are no pi--pi ring interactions in either of the structures. The aminium side chain conformations differ significantly between the two structures, reflecting the conformational ambivalence of the tryptaminium cation, as found also in the benzoate salts.

Effect of water management practice on pesticide behavior in paddy water

The fate and transport of three herbicides commonly used in rice production in Japan were compared using two water management practices. The herbicides were simetryn, thiobencarb and mefenacet. The first management practice was an intermittent irrigation scheme using an automatic irrigation system (AI) with a high drainage gate and the second one was a continuous irrigation and overflow drainage scheme (CI) in experimental paddy fields. Dissipation of the herbicides appeared to follow first order kinetics with the half-lives (DT₅₀) of 1.6-3.4 days and the DT₉₀ (90% dissipation) of 7.4-9.8 days. The AI scheme had little drainage even during large rainfall events thus resulting in losses of less than 4% of each applied herbicide through runoff. Meanwhile the CI scheme resulted in losses of about 37%, 12% and 35% of the applied masses of simetryn, thiobencarb and mefenacet, respectively. The intermittent irrigation scheme using an automatic irrigation system with a high drainage gate saved irrigation water and prevented herbicide runoff whereas the continuous irrigation and overflow scheme resulted in significant losses of water as well as the herbicides. Maintaining the excess water storage is important for preventing paddy water runoff during significant rainfall events. The organic carbon partition coefficient K_oc seems to be a strong indicator of the aquatic fate of the herbicide as compared to the water solubility (S_W). However, further investigations are required to understand the relation between K_oc and the agricultural practices upon the pesticide fate and transport. An extension of the water holding period up to 10 days after herbicide application based on the DT₉₀ from the currently specified period of 3-4 days in Japan is recommended to be a good agricultural practice for controlling the herbicide runoff from paddy fields. Also, the best water management practice, which can be recommended for use during the water holding period, is the intermittent irrigation scheme using an automatic irrigation system with a high drainage gate. © 2006 Elsevier B.V. All rights reserved.

Behavior of simetryn and thiobencarb in the plough zone of rice fields

The behavior of simetryn and thiobencarb in flooded rice soil was investigated in a 2-year study. The concentrations of simetryn and thiobencarb were in the hundreds of μg kg^-1 in the top soil layer (0-5 cm) and became significantly lower in tens of μg kg^-1 in the deeper soil layers (5-10 and 10-15 cm). The half-lives of the two herbicides were also shorter (36 and 17 days for simetryn and thiobencarb, respectively) in the top soil layer, as they were most affected by environmental conditions, compared with corresponding values of 82 and 69 days in the 5-10 cm soil layer. Simetryn concentration was stable, while thiobencarb's half-life was 165 days in the 10-15 cm layer. About 35% of the applied mass of simetryn and thiobencarb were found in the rice soil compartment.

Excess water storage depth - A water management practice to control simetryn and thiobencarb runoff from paddy fields

Experiments were carried out to verify the effectiveness of the excess water storage depth (EWSD) in reducing runoff losses of simetryn and thiobencarb from paddy fields upon appreciable rainfall events. A paddy plot having an EWSD of 2 cm was effective in controlling runoff with the herbicide losses of less than 1% of the applied herbicides. Meanwhile, a plot with 0-cm EWSD lost 18.1 and 3.7% of the applied mass of simetryn and thiobencarb, respectively. Therefore, an appropriate EWSD is essential during the recommended 7-day water holding period in order to completely hold the water inside the field in case of rainfall.

Applicability of ELISA in pesticide monitoring to control runoff of bensulfuron-methyl and simetryn from paddy fields

The applicability of ELISA kits was evaluated as an alternative to monitor bensulfuron-methyl and simetryn behavior in paddy water under intermittent (Plot 1) and continuous (Plot 2) irrigation schemes. Simetryn concentrations in both plots decreased exponentially from the peak of the first day. However, the simetryn kit systematically underestimated by a factor of 0.79 as compared to the GC method. Bensulfuron-methyl concentrations exhibited similar dissipation kinetics in paddy water and the drainage water. The bensulfuron-methyl kit was capable of distinguishing spatial variations of concentrations in the paddy field. The ELISA kits clearly indicated differences in the loss of both herbicides between the two plots and therefore may be useful for evaluating the water management practice of pesticide runoff control in paddy fields.

Pesticide discharge and water management in a paddy catchment in Japan

Concentrations of several pesticides were monitored in a paddy block and in the Kose river, which drains a paddy catchment in Fukuoka prefecture, Japan. Detailed water management in the block was also monitored to evaluate its effect on the pesticide contamination. The concentrations of applied pesticides in both block irrigation channel and drainage canal increased to tens of μg/L shortly after their applications. The increase in pesticide concentrations was well correlated with the open of irrigation and drainage gates in the pesticide-applied paddy plots only 1–3 days after pesticide application. High concentration of other pesticides, mainly herbicides, was also observed in the inflow irrigation and drainage waters, confirming the popularity of early irrigation and drainage after pesticide application in the area. The requirement of holding water after pesticide application (as a best management practice) issued by the authority was thus not properly followed. In a larger scale of the paddy catchment, the concentration of pesticides also increased significantly to several μg/L in the water of the Kose river shortly after the start of the pesticide application period either in downstream or mid–upstream areas, confirming the effect of current water management to the water quality. More extension and enforcement on water management should be done in order to control pesticide pollution from rice cultivation in Japan.

Fate and transport of bensulfuron-methyl and imazosulfuron in paddy fields: Experiments and model simulation

Experiments were conducted to determine the fate of bensulfuron-methyl (BSM) and imazosulfuron (IMS) under paddy conditions. Initially, laboratory experiments were conducted and the photolysis half-lives of the two herbicides were found to be much shorter than their hydrolysis half-lives in aqueous solutions. In the aerobic water–soil system, dissipation followed first-order kinetics with water half-lives of 9.1 and 11.0 days and soil half-lives of 12.4 and 18.5 days (first phase) and 35.0 and 44.1 days (second phase) for bensulfuron-methyl and imazosulfuron, respectively. However, the anaerobic soil half-lives were only 12.7 and 9.8 days for BSM and IMS, respectively. The values of K d were determined to be 16.0 and 13.8 for BSM and IMS, respectively. Subsequent field measurements for the two herbicides revealed that dissipation of both herbicides in paddy water involved biphasic first-order kinetics, with the dissipation rates in the first phase being much faster than those in the second phase. The dissipation of bensulfuron-methyl and imazosulfuron in the paddy surface soil were also followed biphasic first-order kinetics. These results were then used as input parameters for the PCPF-1 model to simulate the fate and transport of BSM and IMS in the paddy environment (water and 1-cm surface soil layer). The measured and simulated values agreed well and the mass balance error during the simulation period was −1.2 and 2.8% of applied pesticide, respectively, for BSM and IMS.

Pesticide exposure assessment in rice paddy areas: A Japanese perspective

This chapter provides an overview of the Japanese regulatory issues regarding pesticide use in rice paddies and an introduction of the new pesticide registration program. In addition, the experience of the environmental monitoring of pesticides and the modeling approaches used for the calculation of predicted environmental concentrations (PECs) in surface water and ground water systems adjacent to rice paddies in Japan are also discussed. Japan has been one of the major pesticide users in the world. Although having a long history in rice cultivation, the pesticide exposure assessment for paddy rice production received less attention compared with EU and US. Applications of up-to-date techniques and the development of realistic assessment procedures under specific climatic conditions as well as mitigation management practices for controlling pesticide contamination are important for an environmental-friendly rice production. Through the international cooperation and research exchanges, advances in pesticide risk assessment for rice paddies in Asian region and other rice-growing areas in the world would contribute to sustainable rice production. Transplanting of rice seedlings grows almost all rice paddies in Japan. The land preparation starts around April and June, and the harvest season lasts from August to October depending on the region and the rice varieties. Most of the rice paddies are treated with herbicides and other crop protection products, such as fungicides and insecticides that are applied during the crop season accordingly. Newly developed insecticides and fungicides are also applied during seedbed preparation.

Behavior of simetryn and thiobencarb in rice paddy lysimeters and the effect of excess water storage depth in controlling herbicide run-off

Eight small-scale lysimeters with different excess water storage depths (EWSDs) were used to investigate the behavior of two herbicides, simetryn and thiobencarb, under paddy conditions. The concentration of simetryn dissipated similarly in all the lysimeters, while the thiobencarb concentration varied significantly because thiobencarb can adsorb onto the dissolved organic matter in a manure slurry, which was applied to six of the lysimeters. The herbicide losses (the percentage of the applied mass) from the lysimeters were reversely proportional with the EWSD. The correlation was stronger for simetryn than for thiobencarb. An appropriate EWSD is required to effectively prevent herbicide run-off from the paddy field, especially when a rainfall event occurs soon after herbicide application.

Impacts of tillage and application methods on atrazine and alachlor losses from upland fields: Research paper

The effects of tillage practises and the methods of chemical application on atrazine and alachlor losses through run-off were evaluated for five treatments: conservation (untilled) and surface (US), disk and surface, plow and surface, disk and preplant-incorporated, and plow and preplant-incorporated treatments. A rainfall simulator was used to create 63.5 mm h^-1 of rainfall for 60 min and 127 mm h^-1 for 15 min. Rainfall simulation occurred 24-36 h after chemical application. There was no significant difference in the run-off volume among the treatments but the untilled treatment significantly reduced erosion loss. The untilled treatments had the highest herbicide concentration and the disk treatments were higher than the plow treatments. The surface treatments showed a higher concentration than the incorporated treatments. The concentration of herbicides in the water decreased with time. Among the experimental sites, the one with sandy loam soil produced the greatest losses, both in terms of the run-off volume and herbicide loss. The US treatments had the highest loss and the herbicide incorporation treatments had smaller losses through run-off as the residue cover was effective in preventing herbicide losses. Incorporation might be a favorable method of herbicide application to reduce the herbicide losses by run-off.

Crystal structures and hydrogen bonding in the morpholinium salts of four phenoxyacetic acid analogues

The anhydrous salts morpholinium (tetrahydro-2-H-1,4-oxazine) phenxyacetate, C4H10NO+ C8H7O3- (I), (4-fluorophenoxy)acetate, C4H10NO+ C8H6FO3- (II) and isomeric morpholinium (3,5-dichlorophenoxy)acetate (3,5-D) (III) and morpholinium (2,4-dichlorophenoxy)acetate (2,4-D), C4H10NO+ C8H5Cl2O3- (IV), have been determined and their hydrogen-bonded structures are described. In the crystals of (I), (III) and (IV), one of the the aminium H atoms is involved in a three-centre asymmetric cation-anion N-H...O,O' R2/1(4) hydrogen-bonding interaction with the two carboxyl O-atom acceptors of the anion. With the structure of (II), the primary N---H...O interaction is linear. In the structures of (I), (II) and (III), the second N-H...O(carboxyl) hydrogen bond generates one-dimensional chain structures extending in all cases along [100]. With (IV), the ion pairs are linked though inversion-related N-H...O hydrogen bonds [graph set R2/4(8)], giving a cyclic heterotetrameric structure.

Selective herbicide strategies for use in Australian desmanthus seed crops

Grass and broad-leaved weeds can reduce both yields and product marketability of desmanthus (Desmanthus virgatus) seed crops, even when cultural control strategies are used. Selective herbicides might economically control these weeds, but, prior to this study, the few herbicides tolerated by desmanthus did not control key weed contaminants of desmanthus seed crops. In this study, the tolerance of desmanthus cv. Marc to 55 herbicides used for selective weed control in other leguminous crops was assessed in 1 pot trial and 3 Queensland field trials. One field trial assessed the tolerance of desmanthus seedlings to combinations of the most promising pre-emergent and post emergent herbicides. The pre-emergent herbicides, imazaquin, imazethapyr, pendimethalin, oryzalin and trifluralin, gave useful weed control with very little crop damage. The post-emergent herbicides, haloxyfop, clethodim, propyzamide, carbetamide and dalapon, were safe for controlling grass weeds in desmanthus. Selective post-emergence control of broad-leaved weeds was achieved using bentazone, bromoxynil and imazethapyr. One trial investigated salvaging second-year desmanthus crops from mature perennial weeds, and atrazine, terbacil and hexazinone showed some potential in this role. Overall, our results show that desmanthus tolerates herbicides which collectively control a wide range of weeds encountered in Queensland. These, in combination with cultural weed control strategies, should control most weeds in desmanthus seed crops.

Calotrope (Calotropis procera) control

Calotrope [Calotropis procera (Aiton) W.T.Aiton] is an exotic shrub or small tree species that is currently invading the tropical savannahs of northern Australia. A chemical trial involving 11 herbicides and four application methods (foliar, basal bark, cut stump and soil applied) was undertaken to identify effective chemicals to control calotrope. Of the foliar herbicides tested, imazapyr provided 100% mortality at the rates applied, and the higher rate of metsulfuron-methyl killed 100% of the treated plants. The herbicides 2,4-D butyl ester, fluroxypyr, triclopyr and triclopyr/picloram killed greater than 80% of the plants when applied by a basal bark or cut stump (when cut 5cm above ground level) method of application. Plants cut close to ground level (5cm) were controlled more effectively than plants cut 20cm above ground level. Chemical control (foliar and cut stump spraying) is a cost effective tool to treat calotrope densities <800plants/ha. Adoption of pasture management practices that promote perennial grasses, in conjunction with strategic chemical control, would further increase the effectiveness and reduce the costs of controlling vast areas of this weed.