Degradation of insecticides used for indoor spraying in malaria control and possible solutions
- Mthokozisi M Sibanda†1,
- Walter W Focke†1Email author,
- Frederick JWJ Labuschagne1,
- Lumbidzani Moyo1,
- Nontete S Nhlapo1,
- Arjun Maity2,
- Herminio Muiambo1, 3,
- Pedro MassingaJr1, 3,
- Nico AS Crowther4,
- Maureen Coetzee5 and
- Gordon WA Brindley1
© Sibanda et al; licensee BioMed Central Ltd. 2011
Received: 25 July 2011
Accepted: 18 October 2011
Published: 18 October 2011
The insecticide dichloro-diphenyl-trichloroethane (DDT) is widely used in indoor residual spraying (IRS) for malaria control owing to its longer residual efficacy in the field compared to other World Health Organization (WHO) alternatives. Suitable stabilization to render these alternative insecticides longer lasting could provide a less controversial and more acceptable and effective alternative insecticide formulations than DDT.
This study sought to investigate the reasons behind the often reported longer lasting behaviour of DDT by exposing all the WHO approved insecticides to high temperature, high humidity and ultra-violet light. Interactions between the insecticides and some mineral powders in the presence of an aqueous medium were also tested. Simple insecticidal paints were made using slurries of these mineral powders whilst some insecticides were dispersed into a conventional acrylic paint binder. These formulations were then spray painted on neat and manure coated mud plaques, representative of the material typically used in rural mud houses, at twice the upper limit of the WHO recommended dosage range. DDT was applied directly onto mud plaques at four times the WHO recommended concentration and on manure plaques at twice WHO recommended concentration. All plaques were subjected to accelerated ageing conditions of 40°C and a relative humidity of 90%.
The pyrethroids insecticides outperformed the carbamates and DDT in the accelerated ageing tests. Thus UV exposure, high temperature oxidation and high humidity per se were ruled out as the main causes of failure of the alternative insecticides. Gas chromatography (GC) spectrograms showed that phosphogypsum stabilised the insecticides the most against alkaline degradation (i.e., hydrolysis). Bioassay testing showed that the period of efficacy of some of these formulations was comparable to that of DDT when sprayed on mud surfaces or cattle manure coated surfaces.
Bioassay experiments indicated that incorporating insecticides into a conventional paint binder or adsorbing them onto phosphogypsum can provide for extended effective life spans that compare favourably with DDT's performance under accelerated ageing conditions. Best results were obtained with propoxur in standard acrylic emulsion paint. Similarly, insecticides adsorbed on phosphogypsum and sprayed on cattle manure coated surfaces provided superior lifespans compared with DDT sprayed directly on a similar surface.
KeywordsIndoor residual spray DDT pyrethroid carbamate stabilization
The World Health Organization (WHO) Global Malaria Action Plan promotes indoor residual spraying (IRS) as a primary operational vector control intervention to reduce and ultimately eliminate malaria transmission. In some southern African countries DDT is regarded as the most effective insecticide for this purpose. Depending on the dosage and substrate nature, DDT retains its efficacy against malaria vectors for up to 12 months. In South Africa DDT was temporarily replaced with the pyrethroid deltamethrin between 1996 and 1999. However, DDT was reintroduced in 2000 when malaria transmission reached epidemic proportions. The failure of the pyrethroid was attributed to the return of the major vector mosquito, Anopheles funestus that was shown to be resistant to pyrethroids but fully susceptible to DDT [1, 2]. Other WHO-approved pyrethroid, organophosphate and carbamate insecticides are limited in effective IRS residual life. Furthermore, repeated application of these alternatives is required in order to provide year-round protection and this significantly increases the costs of IRS . Formulations based on micro-encapsulated insecticides have been tested with great success [4–7]. These results show that shielding the insecticides from the outside environment stabilizes them against premature degradation. However, the higher costs associated with such formulations may limit their widespread implementation as replacements for DDT in IRS.
The stability of WHO-approved insecticides for IRS is affected by the pH of the environment [8–14], temperature [15–19], exposure to ultraviolet (UV) light [20–30] and the availability of degrading bacteria [31–36]. Pyrethroids, organophosphates and carbamates degrade via hydrophilic attack of the carboxylic and carbamic ester linkages [11–13]. DDT undergoes alkaline dechlorination to yield DDE .
On thermal exposure, phenyl carbamates representative of bendiocarb and propoxur degrade to the corresponding phenol and methylisocyanate . Pyrethroids transform by isomerization, ester cleavage and primary oxidation of the final products [16, 17]. Organophosphates, e.g. malathion, initially isomerize to S-alkyl organophosphates before they eventually decompose . The primary step in thermal decomposition of p,p'-DDT is the elimination of HCl, resulting in the formation of p,p'-DDE at 152°C . DDE starts to volatilize at the onset of the process. The decomposition temperature is dependent on the type of DDT, for o,p'-DDT the decomposition starts at higher temperatures.
All the insecticides classes, except for pyrethroids to some extent, are degraded by exposure to ultraviolet light. Fenitrothion undergoes photo-oxidation on the benzene methyl group to form a carboxylic acid group. It may also undergo oxidation on the ─P═S moiety group to form the oxon and ester cleavage to form the corresponding phenol . Malathion is generally stable to photolysis. This may be due to a lack of chromophores to absorb radiation in the UV- range . Pirimiphos-methyl photodegrades rapidly forming 2-diethylamino-6-methylpyrimidin-4-ol as the major degradation product . Carbamate photodegradation involves the cleavage of the carbamic acid ester to form the corresponding alkyl phenyl ether or alkyl phenol ether . Carbamates isomerize on irradiation through the photo-Fries re-arrangement. Photo decomposition of carbamates also produces cholinesterase inhibitors . DDT undergoes homolytic cleavage of the C─Cl bond on the trichloromethyl group to form DDD as the product . DDE may be produced due to exothermic effects of the initial photodechlorination stage. The overall photodechlorination is proposed to be dominated by the sequential dechlorination pathway with each successive dehalogenation proceeding more slowly. Apart from etofenprox, all pyrethroids are structurally similar. They all feature the characteristic carboxylic ester moiety, the dihalogen substituted vinyl moiety and the phenoxy ether group. Etofenprox only contains the phenoxy ether group. The carboxylic ester moiety is susceptible to photodegradation and hence decarboxylation of these insecticides is the main route of photodegradation [26, 27]. However photodecarboxylation of these pyrethroids is a minor transformation process accounting for not more than 15% of the transformation products . The amount of decarboxylation depends on the halogen substituents on the vinyl moiety, i.e. the more electronegative the halogen the more the decarboxylation. The main process of transformation of these pyrethroids is photo-isomerization (cis/trans and E/Z) on the triplet diradicals formed on exposure to ultraviolet light (>300 nm), e.g. deltamethrin , cypermethrin and cyhalothrin . Cyfluthrin is subject to photolysis rapidly forming 4-fluorophenoxybenzaldehyde via ester hydrolysis and the release of cyanide ion from the corresponding cyanohydrin .
Extensive work has been done on the fundamentals of insecticide biodegradation to develop bioremediation techniques to detoxify contaminated environments . Microbiological degradation of insecticides relies on the availability of organisms that can secrete specific degrading enzymes. Bacteria and fungi have the ability to produce these enzymes under both aerobic and anaerobic conditions. Carbamates, pyrethroids and organophosphates have a common ester moiety that provides a route for bacterial-mediated enzymatic biotransformation. The enzyme groups that are able to hydrolyse these ester moieties include carboxyesterases for carbamic and carboxylic esters, and phosphotriesterases and carboxylesterases for triphosphate esters . DDT is degraded by oxygenases and dehydrogenase enzymes . A period of adaptation is required before degrading microbes manage to establish themselves and significant degradation of the insecticide is observed . This acclimation period entails the building of viable microbial colonies that have a capacity to induce enhanced degradation . The length of the acclimation period is also affected by the availability of suitable metabolic substrates for growth. These can be a carbon source, a mineral nutrient source, or both. The presence of alternative carbon substrates and nutrients generally increases the rate of biodegradation. This is supported by the observed increase in the rate of DDT degradation in highly fertilized soils .
Mineral powders such as bentonite, gypsum, montmorillonite, kaolin, attapulgite, diatomite etc. have been used as insecticide carriers in granular insecticide formulations [37, 38]. These minerals have the ability to slowly release the adsorbed insecticide into the environment [39, 40]. Lagaly  presented an excellent review on pesticide-clay interactions and formulations relevant to formulating insecticide laden clay formulations.
Impurities can mediate catalytic degradation of insecticides adsorbed on soil surfaces. Stability can be improved by deactivating surface active sites responsible . Additives such as polyethylene glycol are reportedly very effective deactivators. A useful property of mineral powder carriers is that they can stabilize photolabile and thermolabile insecticides [43–45].
Our ultimate aim is to develop long-lasting, "green" and cost effective alternatives to DDT for IRS. This paper reports on investigations directed towards finding ways to extend the active life of insecticides formulated in environmentally stable, pesticide-based "whitewash" or equivalent "paint". The goals of this investigation were to overcome the time-limited effectiveness of current WHO-approved DDT alternatives by evaluating the interactions between selected insecticides with the micro-environment on which they are applied and also with low-cost paint ingredients.
Insecticides tested and WHO recommended dosage range for IRS
IRS dosage g/m2
1 - 2
0.1 - 0.4
1 - 2
0.02 - 0.03
A sulphonated mimosa extract (Mimosa WS supplied by Mimosa Extract Company) was used as dispersant. Makeean Polymers MCP 503 acrylic copolymer emulsion was used as binder. The emulsion had a solids content of 56 wt.% and a pH of 7.5 - 8.5.
Ethanol (96% Univar rectified), methanol (Univar) and acetone (Univar) were supplied by Merck. Two soil samples were used to prepare substrate surfaces. They were collected at Thomo (Clay 10%, Silt 25.0% and coarse sand 59.8%) and Makoya (clay 10%, silt 10% and coarse sand 95.1%) locations in Mozambique. The pH values of the soil samples were 7.1 and 6.5 respectively.
Accelerated ageing mediated by temperature, ultra-violet light or high humidity
Polytetrafluoroethylene (PTFE) infrared sample cards supplied by Life and Analytical Sciences (PTY) Ltd were used as sample holders. PTFE was chosen as substrate on account of its chemical inertness, UV and temperature stability as well as its transparency in the infrared range 1300 cm-1 to 3400 cm-1 wave numbers. Neat insecticide films were deposited on the substrate by coating it with a 1 wt.% solution of the active in acetone and allowing the solvent to evaporate.
The state of the insecticides deposited on the Teflon substrates was followed as a function of ageing time using Fourier Transform Infrared (FTIR) spectroscopy. A Perkin Elmer Spectrum 100 spectrometer was used in transmission mode. The resolution was 1 cm-1 and 20 scans were recorded per sample.
A Labcon economy type EFDO oven, set at 80°C, was used for high temperature ageing. Samples were exposed to this elevated temperature for consecutive 50 h periods. FTIR spectra were recorded after each exposure period. A Labcon model FSIM forced circulation incubator was used for humidity ageing. The incubator controlled the temperature to within ±0.2°C and humidity to within ± 2% ℜH. The samples were exposed to a relative humidity of 90% at 60°C for 168 h. Accelerated artificial weathering was conducted in a QUV tester fitted with A340 UV lamps. A dry cycle was used with the temperature set at 63°C and an irradiance of 0.67 W.m-2.
Hydrolytic stability of the insecticides
Since most insecticides are effectively insoluble in water, the following procedure was used to explore the effect of mineral powders on hydrolytic stability. Stock solutions containing ca. 1% insecticide were prepared by first dissolving 8 g bendiocarb or alphacypermethrin in 800 g acetone and then adding 32 g of distilled water. Mineral powder (1 g) was added to two sets of six Schott glass bottles. To this was added 21 g of the respective insecticide stock solutions. The top of the bottles were sealed with Parafilm before capping and then wrapped in aluminium foil to protect against light exposure. The bottles were agitated on a shaker table at frequency of 180 cycles per minute during the ageing period at ambient conditions (temperature ranging from ca. 15°C to 25°C). Two sets of solutions (without mineral powders) for each insecticide were used as reference and control standards respectively. The Reference sample was stored in a fridge and the (negative) Control sample was kept under the same conditions as the test samples. A small amount of sodium ethoxide, a strong alkali, was added to another pair of Schott glass bottles containing the bendiocarb and alphacypermethrin stock solutions. These samples provided a positive control and were prepared in order to confirm the instability of both insecticides in highly alkaline environments.
The degradation of the insecticide in the presence or absence of mineral powders was followed using a Varian Star model 3400CX gas chromatograph fitted with an Agilent HP 5 GC column. The column length was 30 m and the internal diameter 0.25 mm with a film thickness of 0.25 μm. The carrier gas was helium and the gas split ratio was 1:30. A flame ionization detector was used. For bendiocarb the initial oven temperature was 120°C, a holding time of 1 minute, a ramp rate of 25°C.min-1, final temperature of 250°C and a final holding time of 10 min. The injector temperature was 200°C while the detector temperature was set at 265°C. For alphacypermethrin the initial oven temperature was set at 245°C and the temperature was immediately ramped at a rate of 25°C.min-1 to the final temperature of 275°C where it was held for 10 minutes. The injector and detector temperatures were both set at 250°C.
Spray surfaces and insecticide formulations for ageing and bio-assaying
Soil samples were mixed with warm water to form a thick paste. This paste was then packed in substrate holders made from high density polyethylene (HDPE). These were round shallow dishes with diameter 11.6 cm and depth 2 cm or diameter 15.5 cm and depth 2.5 cm. The mud substrates were then oven dried at 90°C for 24 h. One set of the dried soil plaques was coated with fresh cattle manure diluted with some water. These represented the microbiologically active surfaces typically found in rural mud houses.
Preparation of spray "paints"
Paints were prepared using alphacypermethrin (pyrethroid), bendiocarb and propoxur (carbamates) and DDT (organochlorine). Organophosphates were excluded because they were considered too unstable. Insecticides were dissolved in just enough acetone to completely dissolve the insecticides. Since the insecticides are all water insoluble, the insecticides precipitated on the gypsum when the solution was dispersed into the phosphogypsum slurry. Next, dispersant was added at a loading of 2 wt.% based on the mass of gypsum used. This level was chosen on the basis of its viscosity reducing effect on a 50 wt.% phosphogypsum slurry. These dispersion formulations were sprayed on mud plaques. Experiments conducted at a later stage established that more stable dispersions were obtained by a slight modification of the procedure. In this method the insecticide was dissolved in just sufficient acetone to allow complete wetting of the dry phosphogypsum powder. This mixture was then slurried into water using vigorous stirring and then adding the same amount of dispersant. This second set of dispersion formulations was sprayed onto the cattle manure-coated mud plaques.
The following three types of "paints" formulations were prepared and tested:
Gypsum "white wash". Insecticide-coated phosphogypsum slurry (50 wt.% solids with 1 wt.% dispersant) was used as is. The final insecticide content based on dry solids was 0.37 wt.% alphacypermethrin and 9 wt.% bendiocarb. The dispersions were sprayed on soil surfaces and cattle manure coated surfaces.
Gypsum "white wash" with minimal acrylic binder. Phosphogypsum (45 wt.%), paint binder (4.5 wt.%), dispersant (0.9 wt.%), water (45 wt.%) plus bendiocarb (4.5 wt.%) was used. The final insecticide content based on dry solids was 8 wt.%. This "paint" was sprayed on the mud surfaces. The idea behind adding the acrylic binder was to improve adhesion of the insecticide to the house wall surface.
Acrylic paint. Carbamate insecticides (bendiocarb or propoxur), dissolved in a minimal amount of acetone, were mixed into the neat acrylic emulsion. The final insecticide content was 15.2 wt.% based on dry solids. This "paint" was sprayed on standard soil surfaces.
The insecticide "paints" were deposited on the substrates using an Aircraft Pneumatic Systems, Model SG AS 1001A spray gun. The feed to the spray gun was by gravity. The nozzle diameter was 1.4 mm and the working pressure 2 bar. The spray pattern was adjusted such that the widest possible spray width was achieved. A smaller Aircraft Pneumatic Systems Model SG A138 spray gun was used to spray the DDT acetone solutions. The feed to the spray gun was via suction. This nozzle diameter was 0.8 mm and a working pressure 3.45 bar. The compressed air used for spraying was tapped from a 6 bar compressed air line via a common manifold.
Each "paint" was sprayed onto soil plaques and cattle manure coated surfaces. Triplicate samples of each type was produced and tested. Since the present purpose was to study degradation under accelerated laboratory conditions, the final insecticide loading was set at twice the upper limit of the WHO recommended dosages  (Table 1). DDT was sprayed directly onto the standard soil surface and cattle manure coated surface as a 10 wt.% solution in acetone. Four times the recommended amount of DDT was employed on the soil substrates because it performed poorly when tested at twice the upper limit.
The treated surfaces were subjected to accelerated ageing in a humidity cabinet set at 90% relative humidity and a temperature of 40°C. WHO bioassays methods  were used to periodically track the residual efficacy against mosquitoes. In these tests, 25 non-blood-fed female Anopheles arabiensis mosquitoes (KGB colony housed at the National Institute for Communicable Diseases, Johannesburg), 3-5 days old, were exposed for 30 minutes to samples of the treated or untreated substrate surfaces. Mortality rates were recorded 24 hours after initial exposure of the triplicates for each treated surface.
FTIR recorded performance under accelerated ageing conditions
UV light exposure
The temporal changes in the FTIR spectra for DDT are presented in Figure 2B. The strongest absorption band for DDT is the aromatic C-C in-ring stretch mode located at ca. 1500 cm-1. It is still present after 50 h of exposure but has completely disappeared after 100 h irradiation. The appearance of two new absorption bands 2355 and 2365 cm-1 after merely 50 h UV light exposure indicate the onset of UV mediated degradation. This doubled dominated in the spectra recorded after 100 h and 150 h UV light exposure. The increased intensity of the absorption band at 2968 cm-1 suggests that the aromatic rings were oxidized to phenols or quinones.
The absorption bands characteristic of fenitrothion disappeared within the first 50 h of ageing (Figure 2C). The spectrum of the degraded residue is consistent with the formation of phenols (ca. 2970 cm-1) and phosphates (ca. 2343 cm-1). Bendiocarb also degraded rapidly when exposed to UV light (Figure 2d). The strong absorption peak characteristic of the carbamate carbonyl has completely disappeared after 50 h of irradiation.
Effect of mineral powder on insecticide hydrolysis rates
DDT (31.3) < bendiocarb in binder (38.3) ≈ alphacypermethrin on gypsum (38.7) ≈ bendiocarb on gypsum (39.4) ≈ bendiocarb on gypsum with paint binder (39.6) < propoxur in acrylic paint binder (50.3)
However, the 95% confidence interval for DDT effective life time overlaps with that for all the other treatments except propoxur in the acrylic binder. This means that the difference in performance between DDT and the other paints on mud surfaces is not statistically significant. However, this outcome applies specifically to the procedure used for preparing the dispersion applied to the mud surfaces.
DDT showed similar performance on the dung coated mud surfaces with an estimated active time of 29.3 days and a 95% confidence interval of 25.3 days to 33.4 days. The overall compositions of the insecticide-on-gypsum slurries sprayed onto the mud and dung coated mud samples were identical. However, the improved preparation method was used in the latter case. Therefore it is not possible to make direct comparisons of the performance achieved on the dung surface surfaces with those found on the corresponding mud surfaces. However, mortality rates of 100% were achieved even after seven months of ageing for both the alphacypermethrin-on-gypsum and bendiocarb-on-gypsum sprayed onto manure-coated surfaces.
Loss of insecticide
where nA is mass flux in kg.m2.s-1; Sh is the dimensionless Sherwood number; DAB is the diffusion coefficient in m2.s-1; PA is the vapour pressure of the insecticide in Pa; z is a characteristic length of the system measured in m the diffusion distance in m, taken here as half the width of the house; R is the gas constant 8.314 J.mol-1.K; T is the absolute temperature in K; and MA is the molar mass of the insecticide expressed in kg.mol-1.
Fenitrothion, 136; pirimiphos-methyl 110; bendiocarb, 11; propoxur 96; malathion 457; DDT, 7726; and alphacypermethrin 319.
where Re is the Reynolds number (VL/v); Sc is the Schmidt number (v/D AB ); v is the kinematic viscosity in m2.s-1.
Typical velocities that could be encountered inside a house range from ca. 0.001 m.s-1 to about 1 m.s-1. Using these values and typical property values for air at ambient conditions reveals that the active life times indicated above could be reduced by 4 to 100 times. This means that, with the possible exception of bendiocarb, the loss of activity of the WHO insecticides experienced in the field cannot be attributed to volatilization! The implication is that the loss of activity over time must be associated with degradation processes.
In general organic insecticides degrade when exposed to elevated temperatures (thermal degradation); sunlight (photodegradation); moisture (e.g. hydrolysis), and microbial attack. The laboratory tests used in this study simulated relatively extreme conditions of temperature, ultra violet light exposure, humidity, alkalinity and microbiologically activity. The temporal performance of neat and stabilized WHO-approved insecticides samples were compared to that of neat DDT. It was found that DDT alternatives stabilized through incorporation in an acrylic binder or precipitated on acidic filler outlasted DDT when applied to dung coated surface and performed at least at a similar level when applied to soil surfaces.
The loss of DDT and carbamate insecticide activity under the ageing condition of 80°C is attributed to a combination of thermal degradation and volatilization. The latter speculation is based on the vapour pressure data for the insecticides (Figure 8). The pyrethroid class of insecticides feature the lowest vapour pressures whilst the organophosphates, carbamates and DDT have the highest, second highest and third highest vapour pressure respectively. The vapour pressure data explains why the pyrethroids are generally less fugitive than the rest of the insecticides under oven ageing conditions conducted at 80°C. The low vapour pressure makes the pyrethroid group of insecticide the least volatile as compared to the rest of the insecticides and hence evaporation is slower than the rest. The present observations, however, suggest that pyrethroids are more stable towards thermal exposure compared with DDT and carbamates.
The chemical transformation of insecticides subjected to UV exposure is quite remarkable. Pyrethroids clearly exhibited significantly greater resilience to UV radiation than the rest of the insecticide classes. Thus the accelerated ageing tests conducted presently indicate that pyrethroids were a far more stable class of insecticides when exposed to typical environmental elements of degradation compared with the other classes of insecticides. This strongly suggests that high temperatures, ultra violet light and humidity are not the dominant mechanisms of oxidative/hydrolytic degradation of insecticides in the field.
This suggests that pH-catalysed hydrolysis is a degradation mechanism that is able to deactivate all the other insecticide classes at a rate that is significantly faster that DDT. Malaria control authorities in South Africa prefer to spray DDT on mud walls commonly found in African rural rondavels whilst they spray pyrethroids on western style painted cement walls . This preference is, in part, due to the fact DDT has the ability to persist longer on mud walls compared to pyrethroids. It is possible that in the field of application, surface chemical and biological properties of the walls being sprayed with the insecticides play a significant role in the breakdown of the insecticides through water mediated hydrolysis.
Dwellings in deep rural areas commonly feature mud and dung coated walls. Bioassays were used to follow the time-dependent efficacy of the stabilized insecticides applied onto such surfaces under accelerated laboratory ageing conditions of high humidity and elevated temperature. The considerable variability in the data makes statistically reliable comparisons difficult. However, the results suggest that the carbamates bendiocarb and propoxur perform well when incorporated into an ordinary paint binder, while bendiocarb and alphacypermethrin precipitated on phosphogypsum also performed well in the accelerated ageing test conducted at 40°C and 90% relative humidity.
Conclusions and recommendations
DDT has a significantly longer persistence than other WHO approved insecticides under IRS field conditions. Comparative tests were performed to track the stability of DDT and alternative insecticides under accelerated laboratory ageing conditions of elevated temperature, ultraviolet light exposure and high humidity. The results suggest that these factors are unlikely causes of the lower persistence of IRS insecticides in the environment. It is likely that water mediated hydrolysis, facilitated by a suitable environmental pH values and/or high bioactivity, are more important. To test this hypothesis, bio-assay experiments were conducted on mud and dung coated samples and aged at high humidity conditions that should favour rapid hydrolysis of the insecticides. It was found that selected insecticides incorporated into a conventional paint binder or adsorbed onto phosphogypsum provided effective life spans comparable to or exceeding that of DDT. Adsorbing an insecticide such as alphacypermethrin phosphogypsum mineral powder provided a suitable buffered pH environment, which minimized pH mediated hydrolysis. An acrylic paint binder stabilized carbamates but led to complete deactivation of the pyrethroids. The acrylic paint option provides for a translucent coating that may be more acceptable to users who do not want to alter the colour of their walls.
The results presented here relate to laboratory conditions. It will be necessary to conduct field trials in malaria invested areas to determine whether the present observations translate to actual field conditions. It is hoped that such trials will be able to shed light on the comparative performance of these formulations under normal field conditions. These findings may allow replacement of DDT, a persistent organic pollutant, with WHO-approved insecticides.
MMS is a postgraduate student studying MEng Chemical Engineering at the University of Pretoria. WWF is supervisor and project leader of this research. A full account of this research work in dissertation form can be found on http://upetd.up.ac.za/ETD-db/ETD-browse/browse.
This work was funded by a grant from the Bill & Melinda Gates Foundation through the Grand Challenges Exploration Initiative. Ryan Norton and Allison Gilbert, Malaria Entomology Research Unit, Wits University, are thanked for carrying out the bioassays.
- Hargreaves K, Koekemoer LL, Brooke BD, Hunt RH, Mthembu J, Coetzee M: Anopheles funestus resistant to pyrethroid insecticides in South Africa. Med Vet Entomol. 2000, 14: 181-189. 10.1046/j.1365-2915.2000.00234.x.View ArticlePubMed
- World Health Organization: Use of DDT in malaria vector control. WHO position statement. Document WHO/HTM/GMP/2011, 1-9
- Sadasivaiah S, Tozan Y, Breman JG: Dichlorodiphenyltrichloroethane (DDT) for indoor residual spraying in Africa: how can it be used for malaria control?. Am J Trop Med Hyg. 2007, 77 (6 suppl): 249-263.PubMed
- Amelotti I, Catala SS, Gorla DE: Experimental evaluation of insecticidal paints against Triatoma infestans (Hemiptera: Reduviidae), under natural climatic conditions. Parasit Vectors. 2009, 2: 30-10.1186/1756-3305-2-30.PubMed CentralView ArticlePubMed
- Alarico AG, Romero N, Hernandez L, Catala S, Gorla D: Residual effect of a micro-encapsulated formulation of organophosphates and piriproxifen on the mortality of deltamethrin resistant Triatoma infestans populations in rural houses of the Bolivian Chaco region. Mem Inst Oswaldo Cruz, Rio de Janeiro. 2010, 105 (Suppl 6): 752-754.View Article
- Mosqueira B, Chabi J, Chandre F, Akogbeto Hougard J-M, Carnevale P, Mas-Coma S: Efficacy of an insecticide paint against malaria vectors and nuisance mosquitoes in West Africa - Part 2: Field evaluation. Malar J. 2010, 9: 341-10.1186/1475-2875-9-341.PubMed CentralView ArticlePubMed
- Mosqueira B, Duchon S, Chandre F, Hougard J-M, Carnevale P, Mas-Coma S: Efficacy of an insecticide paint against insecticide-susceptible and resistant mosquitoes - Part 1: Laboratory evaluation. Malar J. 2010, 9: 340-10.1186/1475-2875-9-340.PubMed CentralView ArticlePubMed
- World Health Organization: Bifenthrin, 2-methylbiphenyl-3-ylmethyl (Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropane-carboxylate. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2010, Geneva, 1-39.
- World Health Organization: Deltamethrin, (S)-α-cyano-3-phenoxybenzyl (1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2010, Geneva, 1-72.
- World Health Organization: Etofenprox, 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2007, Geneva, 19-29.
- Camilleri P: Alkaline hydrolysis of some pyrethroid insecticides. J Agric Food Chem. 1984, 32: 1122-1124. 10.1021/jf00125a048.View Article
- Caldwell SR, Raushel FM: Transition-state structures for enzymatic and alkaline phosphotriester hydrolysis. Biochem. 1991, 30 (Suppl 30): 7444-7450.View Article
- Cristenson I: Alkaline hydrolysis of some carbamic acid esters. Acta Chem Scand. 1964, 18 (Suppl 4): 904-922.View Article
- Wolfe NL, Zepp RG, Paris DF, Baughman GL, Hollis RC: Methoxychlor and DDT degradation in water: rates and products. Environ Sci Technol. 1977, 11: 1077-1081. 10.1021/es60135a003.View Article
- Müller H-M, Stan H-J: Thermal degradation observed with different injection techniques: quantitative estimation by the use of thermolabile carbamate pesticides. J High Res Chromat. 1990, 13: 759-763. 10.1002/jhrc.1240131107.View Article
- Audino PG, Licastro SA, Zerba E: Thermal decomposition and isomerisaion of cis-permethrin and β-cypermethrin in the solid phase. Pest Manag Sci. 2001, 58: 183-189.View Article
- Senneca O, Scherillo F, Nuuziata A: Thermal degradation of pesticides under oxidative conditions. J Anal Appl Pyrolysis. 2007, 80: 61-76. 10.1016/j.jaap.2007.01.002.View Article
- Mcpherson JB, Johnson GA: Thermal decomposition of some phosphorothioate insecticides. Agric Food Chem. 1956, 4 (Suppl 1): 42-49.View Article
- Lubkowski J, Janiak T, Czerminski J, Blazejowski J: Thermoanalytical investigations of some chloro-organic pesticides and related compounds. Thermochimica Acta. 1988, 155: 7-28.View Article
- Ohkawa H, Mikami N, Mayambo J: Photodecomposition of sumithion [O,O dimethyl O (3 methyl 4 nitrophenyl) phosphorothioate]. Agric Biol Chem. 1974, 38 (Suppl 11): 2247-2255.View Article
- Katagi T: Photodegradation of pesticides on plant and soil surfaces. Rev Environ Contam Toxicol. 2004, 182: 1-195. 10.1007/978-1-4419-9098-3_1.PubMed
- FAO: Pirimiphosmethyl, O-2-diethylamino-6-methylpyrimidin-4-yl-O,O-dimethyl phosphorothioate. FAO specifications and evaluations for agricultural pesticides. Food and Agriculture Organisation of the United. 2007, Nations Rome, 1-24.
- Schwack W, Kopf G: Photodegradation of the carbamate insecticide propoxur. Z Lebensm Unters Forsch. 1992, 195: 250-253. 10.1007/BF01202804.View Article
- Crosby DG, Leitis E, Winterlin WL: Photodecomposition of carbamate insecticides. J Agric Food Chem. 1965, 13 (Suppl 3): 204-207.View Article
- Lin C, Chang TC: Photosensitized reduction of DDT using visible light: the intermediates and pathways of dechlorination. Chemosphere. 2007, 66: 1003-1011. 10.1016/j.chemosphere.2006.07.049.View ArticlePubMed
- Ueda K, Gaughan LC, Casida JE: Photodecomposition of resmethrin and related pyrethroids. J Agric Food Chem. 1974, 22 (Suppl 2): 212-220.View ArticlePubMed
- Ruzo LO, Casida JE: Pyrethroid photochemistry: intramolecular sensitization and photoreactivity of 3-Phenoxybenzyl, 3-Phenylbenzyl, and 3-Benzoylbenzyl esters. J Agric Food Chem. 1982, 30: 963-966. 10.1021/jf00113a037.View Article
- Ruzo LO, Krishnamarthy VV, Casida JE, Gohre K: Pyrethroids photochemistry: influence of the chloro(trifluoromethyl)vinyl substituent in cyhalothrin. J Agric Food Chem. 1987, 35: 879-883. 10.1021/jf00078a007.View Article
- Ruzo LO, Holmstead RL, Casida JE: Pyrethroid photochemistry: decamethrin. J Agric Food Chem. 1977, 25 (Suppl 6): 1385-1394.View Article
- Ruzo LO: Involvement of oxygen in the in the photoreactions of cypermethrin and other halogenated pyrethroids. J Agric Food Chem. 1983, 31 (Suppl 5): 1115-1117.
- Singh BK, Walker A: Microbial degradation of organophosphorus compounds. FEM Microbial Rev. 2006, 30: 428-471. 10.1111/j.1574-6976.2006.00018.x.View Article
- Sogorb MA, Vilanova E: Enzymes involved in the detoxification of organophosphorus, carbamate and pyrethroid insecticide through hydrolysis. Toxicol Letters. 2002, 128: 215-228. 10.1016/S0378-4274(01)00543-4.View Article
- Singh BK, Kuhad RC, Singh A, Lal R, Tripathi KK: Biochemical and molecular basis of pesticide degradation by microorganisms. Critical Rev Biotechnol. 1999, 19 (Suppl 3): 197-225.View Article
- Arbeli Z, Fuentes CL: Accelerated biodegradation of pesticides: an overview of the phenomenon, its basis and possible solutions; and a discussion on the tropical dimension. Crop Protection. 2007, 26: 1733-1746. 10.1016/j.cropro.2007.03.009.View Article
- Aislabie J, Lloyd-Jones G: A review of bacterial degradation of pesticides. Aust J Soil Res. 1995, 33: 925-942. 10.1071/SR9950925.View Article
- Boul HL, Garnham ML, Hucke D, Baird D, Aislabie J: Influence of agricultural practices on the levels of DDT and its residues in soil. Environ Sci Technol. 1994, 28 (Suppl 8): 1397-1402.View ArticlePubMed
- Goss GR, Taylor DR, Kallay WB: Granular pesticide formulations. Pesticide formulations and application systems. 15th volume. Edited by: Collins HM, Hall FR, Hopkinson M. 1994, American society for testing and materials, Philadelphia, 114-123. ASTM STP 1268
- Murray HH: Traditional and new applications for kaolin, smectite, and alygorskite: a general overview. Appl Clay Sci. 2000, 17: 207-221. 10.1016/S0169-1317(00)00016-8.View Article
- Atkinson PR: Controlled-release insecticide granules, compared with other soil insecticides, for use against the termite, Macrotermes natalensis Haviland, in the establishment of Eucalyptus plantations. Crop Protect. 1989, 8: 387-396. 10.1016/0261-2194(89)90062-8.View Article
- Bruna F, Pavlovic I, Celis R, Barriga C, Comejo J, Ulibarri MA: Organohydroltalcites as novel supports for the slow release of the herbicide terbuthylazine. Appl Clay Sci. 2008, 42: 194-200. 10.1016/j.clay.2008.02.001.View Article
- Lagaly G: Pesticide-clay interactions and formulations. Appl Clay Sci. 2001, 18: 205-209. 10.1016/S0169-1317(01)00043-6.View Article
- Kallay WB, Goss GR, Stein JA: Use of clay deactivators in granular clay formulations. Pesticide formulations and application systems. 12th volume. Edited by: Devisetty B, Chasin G. 1993, American society for testing and materials, Philadelphia, 201-213. ASTM STP 1146
- Margulies L, Rozen H, Cohen E: Photostabilization of a nitromethylene heterocycle insecticide on the surface of montmorillonite. Clays and Clay Minerals. 1988, 36 (Suppl 2): 159-164.View Article
- El-Nahhal Y, Undabeytia T, Polubesiva T, Mishael YG, Nir S, Rubin B: Organo-clay formulations of pesticides: reduced leaching and photodegradation. Appl Clay Sci. 2001, 18: 309-326. 10.1016/S0169-1317(01)00028-X.View Article
- Casal B, Merino J, Serratos J-M, Ruiz-Hitzky E: Sepiolite-based materials for the photo- and thermal-stabilisation of pesticides. Appl Clay Sci. 2000, 18: 245-254.View Article
- Najera JA, Zaim M: Insecticides for indoor residual spraying. Malaria vector control. WHO/CDS/WHOPES/2001.3. Wld Hlth Org. 2001, Geneva
- World Health Organization: Guidelines for testing mosquito adulticides for indoor residual spraying and treatment of mosquito nets. WHO/CDS/NTD/WHOPES/GCDPP/2006.3. Wld Hlth Org. 2006, Geneva, 1-60.
- Segal-Rosenheimer M, Dubowski Y: Photolysis of thin films of cypermethrin using in situ FTIR monitoring: products, rates and quantum yields. J Photochem Photobiol A: Chem. 2008, 200: 262-269. 10.1016/j.jphotochem.2008.08.004.View Article
- Focke WW: A revised equation for estimating the vapour pressure of low-volatility substances from isothermal thermogravimetric data. J Therm Anal Cal. 2003, 74: 1107-1118.View Article
- Reid RC, Prausnitz JM, Poling BE: The Properties of Gases and Liquids. 1987, McGraw-Hill, New York, Fourth
- World Health Organization: Bendiocarb, 2,2-dimethyl-1,3-benzodioxol-4-yl methylcarbamate. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2009, Geneva, 1-33.
- World Health Organization: Propoxur, 2-isopropoxyphenyl methylcarbamate. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2005, Geneva, 1-25.
- Mensik BJWG: Environmental risk limits for pirimiphosmethyl-methyl. RIVM letter report 601716011/2008, National Institute for Public Health and the Environment. 2008, Netherlands
- FAO: Fenitrothion, O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate. FAO specifications and evaluations for agricultural pesticides. Food and Agriculture Organisation of the United Nations. 2010, Rome, 1-32.
- World Health Organization: Malathion, S-1,2-bis(ethoxycarbonyl)ethyl O,O-dimethyl phosphorodithioate. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2004, Geneva, 1-75.
- Royal Society of Chemistry (Great Britain): The Agrochemicals Handbook. 1991, Royal Society of Chemistry Information Services, Cambridge
- World Health Organization: α-Cypermethrin, A racemic mixture of: (S)-α-cyano-3-phenoxybenzyl-(1R,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-α-cyano-3-phenoxybenzyl-(1S,3S)-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-carboxylate. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2009, Geneva, 16-50.
- World Health Organization: Cyfluthrin, (RS)-α-cyano-4-fluoro-3-phenoxybenzyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2004, Geneva, 1-29.
- World Health Organization: Lambda-Cyhalothrin, a reaction product comprising equal quantities of (S)-α-cyano-3-phenoxybenzyl (Z)-(1R,3R)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate and (R)-α-cyano-3-phenoxybenzyl (Z)-(1S,3S)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclo-propanecarboxylate. WHO specifications and evaluations for public health pesticides. Wld Hlth Org. 2007, Geneva, 1-42.
- Bird RB, Stewart WE, Lightfoot EN: Transport Phenomena. 2007, John Wiley & Son, New York, Revised Second Edition
- Hargreaves K, Hunt RH, Brooke BD, Mthembu J, Weeto MM, Awolola TS, Coetzee M: Anopheles arabiensis and An. quadriannulatus resistance to DDT in South Africa. Med Vet Entomol. 2003, 17: 417-422. 10.1111/j.1365-2915.2003.00460.x.View ArticlePubMed
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.