The development of automated methods for the determination of trace concentrations of carbomate pesticides in water using solid sorbent pre-concentration methods and high performance liquid chromatography /

Several automated reversed-phase HPLC methods have been developed to determine trace concentrations of carbamate pesticides (which are of concern in Ontario environmental samples) in water by utilizing two solid sorbent extraction techniques. One of the methods is known as on-line pre-concentration'. This technique involves passing 100 milliliters of sample water through a 3 cm pre-column, packed with 5 micron ODS sorbent, at flow rates varying from 5-10 mUmin. By the use of a valve apparatus, the HPLC system is then switched to a gradient mobile phase program consisting of acetonitrile and water. The analytes, Propoxur, Carbofuran, Carbaryl, Propham, Captan, Chloropropham, Barban, and Butylate, which are pre-concentrated on the pre-column, are eluted and separated on a 25 cm C-8 analytical column and determined by UV absorption at 220 nm. The total analytical time is 60 minutes, and the pre-column can be used repeatedly for the analysis of as many as thirty samples. The method is highly sensitive as 100 percent of the analytes present in the sample can be injected into the HPLC. No breakthrough of any of the analytes was observed and the minimum detectable concentrations range from 10 to 480 ng/L. The developed method is totally automated for the analysis of one sample. When the above mobile phase is modified with a buffer solution, Aminocarb, Benomyl, and its degradation product, MBC, can also be detected along with the above pesticides with baseline resolution for all of the analytes. The method can also be easily modified to determine Benomyl and MBC both as solute and as particulate matter. By using a commercially available solid phase extraction cartridge, in lieu of a pre-column, for the extraction and concentration of analytes, a completely automated method has been developed with the aid of the Waters Millilab Workstation. Sample water is loaded at 10 mL/min through a cartridge and the concentrated analytes are eluted from the sorbent with acetonitrile. The resulting eluate is blown-down under nitrogen, made up to volume with water, and injected into the HPLC. The total analytical time is 90 minutes. Fifty percent of the analytes present in the sample can be injected into the HPLC, and recoveries for the above eight pesticides ranged from 84 to 93 percent. The minimum detectable concentrations range from 20 to 960 ng/L. The developed method is totally automated for the analysis of up to thirty consecutive samples. The method has proven to be applicable to both purer water samples as well as untreated lake water samples.

A mass spectrometric study of some pesticides /|nK. S. Subramanian. -- 260 St. Catharines, Ont. : [s. n.],

The fragmentation processes in the mass spectra of a series of organophosphorus, organochlorine, thio and dithiocarbamate as well as a number of miscellaneous pesticides have been studied i n detail by using the Bendix timeof- flight, MS-12 single-focussing and MS-30 double-focussing mass spectrometers. Interpretation of all the spectra have been presented; their mode s of dissociation elucidated, aided by metastable transitions wherever possible and the structures of the various f ragmentation species postulated wherever f easible. The fragmentation mechanisms are based on the concepts of inductive, resonance and steric ef~ects. Multiple bond cleavages accompanied by simultaneous bond formation and rearrangement reactions involving cycli c t r ansition states have clarified t he formation of various ions . Due emphasis has been placed on the effect of the functional groups or substituents in altering the mass spectral behaviour of the pesticides as they form the basis for the identifi cation of the otherwise identical pesticides. The organophosphorus pesticides which have been studied include i) the phosphates (eg: DDVP and Phosdrin ); ii) phosphorothionates (eg: Parathion, 0-2, 4 dichloro phenyl 0, O-diethyl thionophosphate); iii) phosphorothioites (eg: Tributyl phosphorotrithioite); i V) phosphorothioates (eg: Ethion) and v) phosphorodithioates (eg: Carbophenolthion). Cleavages and rearrangements of the ester moiety dominate the spectrum of phosdrin while that of DDVP is + dominated by t he fragmentation modes of the (OH30)2P=0 + moiety. Fragmentation §f the (CH30)2P=S characterises the spectrum of (OH30)2"P -Cl while cleavages of the + (C2H50 )2P=S species mark the spectra of parathion and 0-2, 4- di chlorophenyl O, O-diethyl thiophosphate. The 0(, cl eavages of the thioether f unction rather than + cleavages of the (C2H50)2P=S signify the spectrum of carbophenolthion. Tributyl phosphorotrithioite behaves more like an aliphatic hydrocarbon than like the corresponding phosphites. The isopropyl and butyl esters of 2, 4 dichlorophenoxy acetic acid show cleavage and rearrangement ions typical of an ester. In spite of its structural similari ty to pp' - DDT and pp' - DDD, Kalthane has a completely different mass spectral behaviour due to the influence of its hydroxyl function. The thiocarbamate pesticides studied include Eptam and Perbulate. Both are structurally similar but having different alkyl substituents on nitrogen and sulphur. This structurQlsimilarity leads to similar types of (N-C), (O-S) and (S-alkyl cleavages). However, perbulate differs from Eptam in showing a rearrangement ion at mle 161 and in forming an isocyanate ion as the base peak. In Eptam the base peak i s the alkyl ion. The dithiocarbamate, Vegadex, resembles the thiocarbamates in undergoing simple cleavages but it differs from them in having a weak parent ion; in the formation of its base peak and in undergoing a series of rearrangement reactions. The miscellaneous pesticides studied include 1-Naphthalene acetic aCid- methyl ester, Fiperonyl butoxide and Allethrin. The ester i s stable to electron impact and shows only fewer ions. Piper onyl butoxide, a polyether, shows characteristics of an et her, alcohol and aldehyde . Allethrin is regarded as an ester of the type R-C-O-R1 with n R being a substituted cyclopr opane moiety and o Rt, a substituted cyclopentenone mOiety. Accordingly it shows cleavage ions typical of an aliphatic ester and undergoes bond ruptures of the cyclic moieties to give unusual ions. Its base peak is an odd electron ion, quite contrary to expectations.

Combined toxic effects of oil and pesticides on selected marine invertebrates

In recent years, pollution in general and sea water pollution in particular, has become an important topic for national and international considerations. Because of its impact on society, marine pollution has attracted great attention from politicians, administrators, natural scientists and technologists all over the world. To save our environment from further deterioration, it is essential to have an assessment of this problem This thesis involves investigation of the lethal and sub lethal effects of four pesticides and two petroleum oil, individually and in combinations on two commercially important bivalves. Among the four pesticides used two are organophosphates and the other two are organochlorines. Synthetic Pesticides, especially organophosphates and organochlorines have become increasingly important additions to chemical wastes polluting natural aquatic Communities special attention is given in the present investigation to delineate the combined toxic effect of oil and pesticides. The results are presented under different sections to make the presentation meaningful.

Application of primary haemocyte culture of Penaeus monodon in the assessment of cytotoxicity and genotoxicity of heavy metals and pesticides

Lack of shrimp cell lines has hindered the study of pollutants which adversely affects shrimp health and its export value. In this context a primary haemocyte culture developed from Penaeus monodon was employed for assessing the cytotoxicity and genotoxicity of two heavy metal compounds, cadmium chloride and mercuric chloride and two organophosphate insecticides, malathion and monocrotophos. Using MTT assay 12 h IC50 values calculated were 31.09 16.27 mM and 5.52 1.16 mM for cadmium chloride and mercuric chloride and 59.94 52.30 mg l 1 and 186.76 77.00 mg l 1 for malathion and monocrotophos respectively. Employing Comet assay, DNA damage inflicted by these pollutants on haemocytes were evaluated and the pollutants induced DNA damage in >60% of the cells. The study suggested that haemocyte culture could be used as a tool for quantifying cytotoxicity and genotoxicity of aquaculture drugs, management chemicals and pollutants

Historical Development of Organochlorine Pesticides Legislation in Venezuela

Information about organochlorine pesticides legislation in Venezuela was recovered, using the search engine Google. Progress and setbacks was analyzed, with information about imports, exports, inventories, storage sites, controls and actions taken for disposal and participation in international conventions. The country appears to have adequate legislation, however, greater consistency of laws and decrees are required. Update the technical rule is necessary and increases the capacity to monitoring, identification and elimination of organochlorine pesticides.

Bt cotton, pesticides, labour and health - A case study of smallholder farmers in the Makhathini Flats, Republic of South Africa

This paper describes some of the results of a detailed farm-level survey of 32 small-scale cotton farmers in the Makhathini Flats region of South Africa. The aim was to assess and measure some of the impacts (especially in terms of savings in pesticide and labour as well as benefits to human health) attributable to the use of insect-tolerant Bt cotton. The study reveals a direct cost benefit for Bt growers of SAR416 ($51) per hectare per season due to a reduction in the number of insecticide applications. Cost savings emerged in the form of lower requirements for pesticide, but also important were reduced requirements for water and labour. The reduction in the number of sprays was particularly beneficial to women who do some spraying and children who collect water and assist in spraying. The increasing adoption rate of Bt cotton appears to have a health benefit measured in terms of reported rates of accidental insecticide poisoning. These appear to be declining as the uptake of Bt cotton increases. However, the understanding of refugia and their management by local farmers are deficient and need improving. Finally, Bt cotton growers emerge as more resilient in absorbing price fluctuations.

Bt cotton, pesticides, labour and health - A case study of smallholder farmers in the Makhathini Flats, Republic of South Africa

This paper describes some of the results of a detailed farm-level survey of 32 small-scale cotton farmers in the Makhathini Flats region of South Africa. The aim was to assess and measure some of the impacts (especially in terms of savings in pesticide and labour as well as benefits to human health) attributable to the use of insect-tolerant Bt cotton. The study reveals a direct cost benefit for Bt growers of SAR416 ($51) per hectare per season due to a reduction in the number of insecticide applications. Cost savings emerged in the form of lower requirements for pesticide, but also important were reduced requirements for water and labour. The reduction in the number of sprays was particularly beneficial to women who do some spraying and children who collect water and assist in spraying. The increasing adoption rate of Bt cotton appears to have a health benefit measured in terms of reported rates of accidental insecticide poisoning. These appear to be declining as the uptake of Bt cotton increases. However, the understanding of refugia and their management by local farmers are deficient and need improving. Finally, Bt cotton growers emerge as more resilient in absorbing price fluctuations.

Phyto-activity of biocides used to manipulate herbivory: tests of three pesticides on fourteen plant species

1. We tested three pesticides used for field manipulations of herbivory for direct phytoactive effects on the germination and growth of 14 herbaceous plant species selected to provide a range of life-history strategies and functional groups. 2. We report three companion experiments: (A) Two insecticides, chlorpyrifos (granular soil insecticide) and dimethoate (foliar spray), were applied in fully-factorial combination to pot-germinated individuals of 12 species. (B) The same fully-factorial design was used to test for direct effects on the germination of four herbaceous legumes. (C) The molluscicide, metaldehyde, was tested for direct effects on the germination and growth of six plant species. 3. The insecticides had few significant effects on growth and germination. Dimethoate acted only on growth stimulating Anisantha sterilis, Sonchus asper and Stellaria graminea. In contrast, chlorpyrifos acted on germination increasing the germination of Trifolium dubium and Trifolium pratense. There was also a significant interactive effect of chlorpyrifos and dimethoate on the germination of T pratense. However, all. effects were relatively small in magnitude and explanatory power. The molluscicide had no significant effect on plant germination or growth. 4. The small number and size of direct effects of the pesticides on plant performance is encouraging for the use of these pesticides in manipulative experiments on herbivory, especially for the molluscicide. However, a smatt number of direct (positive) effects of the insecticides on some plant species need to be taken into account when interpreting field manipulations of herbivory with these compounds, and emphasises the importance of conducting tests for direct phyto-active effects. (C) 2004 Elsevier GmbH. All rights reserved.

The influence of Langmuir turbulence on the scaling for the dissipation rate in the oceanic boundary layer

A model for estimating the turbulent kinetic energy dissipation rate in the oceanic boundary layer, based on insights from rapid-distortion theory, is presented and tested. This model provides a possible explanation for the very high dissipation levels found by numerous authors near the surface. It is conceived that turbulence, injected into the water by breaking waves, is subsequently amplified due to its distortion by the mean shear of the wind-induced current and straining by the Stokes drift of surface waves. The partition of the turbulent shear stress into a shear-induced part and a wave-induced part is taken into account. In this picture, dissipation enhancement results from the same mechanism responsible for Langmuir circulations. Apart from a dimensionless depth and an eddy turn-over time, the dimensionless dissipation rate depends on the wave slope and wave age, which may be encapsulated in the turbulent Langmuir number La_t. For large La_t, or any Lat but large depth, the dissipation rate tends to the usual surface layer scaling, whereas when Lat is small, it is strongly enhanced near the surface, growing asymptotically as ɛ ∝ La_t^{-2} when La_t → 0. Results from this model are compared with observations from the WAVES and SWADE data sets, assuming that this is the dominant dissipation mechanism acting in the ocean surface layer and statistical measures of the corresponding fit indicate a substantial improvement over previous theoretical models. Comparisons are also carried out against more recent measurements, showing good order-of-magnitude agreement, even when shallow-water effects are important.

Constraints on the spectral distribution of energy and enstrophy dissipation in forced two-dimensional turbulence

We study two-dimensional (2D) turbulence in a doubly periodic domain driven by a monoscale-like forcing and damped by various dissipation mechanisms of the form νμ(−Δ)μ. By “monoscale-like” we mean that the forcing is applied over a finite range of wavenumbers kmin≤k≤kmax, and that the ratio of enstrophy injection η≥0 to energy injection ε≥0 is bounded by kmin2ε≤η≤kmax2ε. Such a forcing is frequently considered in theoretical and numerical studies of 2D turbulence. It is shown that for μ≥0 the asymptotic behaviour satisfies ∥u∥12≤kmax2∥u∥2, where ∥u∥2 and ∥u∥12 are the energy and enstrophy, respectively. If the condition of monoscale-like forcing holds only in a time-mean sense, then the inequality holds in the time mean. It is also shown that for Navier–Stokes turbulence (μ=1), the time-mean enstrophy dissipation rate is bounded from above by 2ν1kmax2. These results place strong constraints on the spectral distribution of energy and enstrophy and of their dissipation, and thereby on the existence of energy and enstrophy cascades, in such systems. In particular, the classical dual cascade picture is shown to be invalid for forced 2D Navier–Stokes turbulence (μ=1) when it is forced in this manner. Inclusion of Ekman drag (μ=0) along with molecular viscosity permits a dual cascade, but is incompatible with the log-modified −3 power law for the energy spectrum in the enstrophy-cascading inertial range. In order to achieve the latter, it is necessary to invoke an inverse viscosity (μ<0). These constraints on permissible power laws apply for any spectrally localized forcing, not just for monoscale-like forcing.