Pesticide absorbance

From the late 1960s until the early 1980s, a large number of worker exposure studies were reported which used the methods of passive dosimetry — that is, methods that measured potential contact with pesticides but did not measure the actual amount of pesticide absorbed by the workers bodies. These studies were extensively reviewed by Wolfe (1976) and later by Davis (1980). 

Plant uptake. Pesticide uptake by plants has not been considered in most modeling efforts. This is primarily due to an almost total lack of quantitative experimental information available to the modeler, and the presumption that the absolute mass of pesticide absorbed by the plant is small compared to the mass remaining in the system. Due to these considerations, modelers have apparently assumed that any inaccuracy in simulation of pesticide fate that results from not considering plant uptake is within the "noise" of inaccuracies produced by other assumptions about the physical, chemical, and biological processes operating in the system. While this assumption is unproven for pesticide absorption, it clearly cannot be accepted for water absorption by the plant (the U(z,t) term in Equation 4). Plant extraction of water greatly influences water flux, which affects pesticide... 

For practical purposes, the energy derived from sunlight does not exceed about 95 kcal/einstein (corresponding to 300 nm) because of absorption by atmospheric ozone (25). Few pesticides absorb appreciable light above about 400 nm, and also the quantum energy available at the longer wavelengths (less than 60 kcal/einstein) is insufficient to break most kinds of chemical bonds commonly found in these compounds... 

Occupational disease, caused by skin contact with toxic substances, represents a major health problem In the United States (1). Dermal exposure of agricultural workers to pesticide agents, of course. Is a particularly pertinent example of this problem. Prediction of the detrimental toxic effects of hazardous chemical exposure Is difficult, however, because of the complexity of the percutaneous absorption process in man and a lack of any consistently Identifiable relatlonshlp(s) between transport rate and chemical properties. In addition, the very diverse approaches, which have been used to measure skin penetration, further complicate the situation since the extrapolation of results to man In his workplace may Involve questionable, non-valldated assumptions. Our specific aim Is to predict accurately the toxicokinetics of occupationally-encountered molecules (e.g., pesticides) absorbed across human skin In vivo. We present... 

In all of our studies where urine has been analyzed, we have collected one total 24-h sample or two 12-h samples over the 5-day period. To determine the amount of the pesticide absorbed, one needs to know both the volume of urine excreted and the concentration of pesticide in that urine. We have observed more than a 10-fold difference in the volume of urine excreted by two different people doing the same type of work. Consequently, trying to determine dose based upon the concentration of a grab sample and a "typical" or "average" excretion volume is unacceptable. Without the total urine sample, two people who have received the same absorbed dose could show a 10-fold difference in concentration of pesticide in their urine and, consequently, in their absorbed dose simply because of dilution. 

The effects of pollution can be direct, such as toxic emissions providing a fatal dose of toxicant to fish, animal life, and even human beings. The effects also can be indirect. Toxic materials which are nonbiodegradable, such as waste from the manufacture of insecticides and pesticides, if released to the environment, are absorbed by bacteria and enter the food chain. These compounds can remain in the environment for long periods of time, slowly being concentrated at each stage in the food chain until ultimately they prove fatal, generally to predators at the top of the food chain such as fish or birds. 

Substances other than enzymes can be immobilized. Examples include the fixing of heparin on polytetrafluoroethylene with the aid of PEI (424), the controUed release of pesticides which are bound to PEI (425), and the inhibition of herbicide suspensions by addition of PEI (426). The uptake of anionic dyes by fabric or paper is improved if the paper is first catonized with PEI (427). In addition, PEI is able to absorb odorizing substances such as fatty acids and aldehydes. Because of its high molecular weight, PEI can be used in cosmetics and body care products, as weU as in industrial elimination of odors, such as the improvement of ambient air quaHty in sewage treatment plants (428). 

Air-poUutant effects on neural and sensory functions in humans vary widely. Odorous pollutants cause only minor annoyance yet, if persistent, they can lead to irritation, emotional upset, anorexia, and mental depression. Carbon monoxide can cause death secondary to the depression of the respiratory centers of the central nervous system. Short of death, repeated and prolonged exposure to carbon monoxide can alter sensory protection, temporal perception, and higher mental functions. Lipid-soluble aerosols can enter the body and be absorbed in the lipids of the central nervous system. Once there, their effects may persist long after the initial contact has been removed. Examples of agents of long-term chronic effects are organic phosphate pesticides and aerosols carrying the metals lead, mercury, and cadmium. 

An enzymatic assay can also be used for detecting anatoxin-a(s). " This toxin inhibits acetylcholinesterase, which can be measured by a colorimetric reaction, i.e. reaction of the acetyl group, liberated enzymatically from acetylcholine, with dithiobisnitrobenzoic acid. The assay is performed in microtitre plates, and the presence of toxin detected by a reduction in absorbance at 410 nm when read in a plate reader in kinetic mode over a 5 minute period. The assay is not specific for anatoxin-a(s) since it responds to other acetylcholinesterase inhibitors, e.g. organophosphoriis pesticides, and would need to be followed by confirmatory tests for the cyanobacterial toxin. 

The main purpose of pesticide formulation is to manufacture a product that has optimum biological efficiency, is convenient to use, and minimizes environmental impacts. The active ingredients are mixed with solvents, adjuvants (boosters), and fillers as necessary to achieve the desired formulation. The types of formulations include wettable powders, soluble concentrates, emulsion concentrates, oil-in-water emulsions, suspension concentrates, suspoemulsions, water-dispersible granules, dry granules, and controlled release, in which the active ingredient is released into the environment from a polymeric carrier, binder, absorbent, or encapsulant at a slow and effective rate. The formulation steps may generate air emissions, liquid effluents, and solid wastes. 

Applicabdity Limitations Photolysis is appropriate for difficult-to-treat chemicals (e.g., pesticides, dioxins, chlorinated organics), nitrated wastes, and those chemicals in media which permits photolyzing the waste. The waste matrix can often shield chemicals from the light (e.g., ultraviolet light absorbers, suspended solids, solid wastes). The photolysis process typically requires pretreatment to remove suspended materials, and the by-products formed may be more toxic than the parent molecules. 

Chemical Tastes (Other) Pesticides-herbicides Activated carbon filter will absorb limited amount. Must continue to monitor the product water closely... 

Skin is also important as an occupational exposure route. Lipid-soluble solvents often penetrate the skin, especially as a liquid. Not only solvents, but also many pesticides are, in fact, preferentially absorbed into the body through the skin. The ease of penetration depends on the molecular size of the compound, and the characteristics of the skin, in addition to the lipid solubility and polarity of the compounds. Absorption of chemicals is especially effective in such areas of the skin as the face and scrotum. Even though solid materials do not usually readily penetrate the skin, there are exceptions (e.g., benzo(Lt)pyrene and chlorophenols) to this rule. 

Plant uptake is one of several routes by which an organic contaminant can enter man s food chain. The amount of uptake depends on plant species, concentration, depth of placement, soil type, temperature, moisture, and many other parameters. Translocation of the absorbed material into various plant parts will determine the degree of man s exposure—i.e., whether the material moves to an edible portion of the plant. Past experience with nonpolar chlorinated pesticides suggested optimal uptake conditions are achieved when the chemical is placed in a soil with low adsorptive capacity e.g., a sand), evenly distributed throughout the soil profile, and with oil producing plants. Plant experiments were conducted with one set of parameters that would be optimal for uptake and translocation. The uptake of two dioxins and one phenol (2,4-dichlorophenol (DCP)) from one soil was measured in soybean and oats (7). The application rates were DCP = 0.07 ppm, DCDD 0.10 ppm, and TCDD = 0.06 ppm. The specific activity of the com-... 

For most chemicals, inhalation is the main route of entry into the body. However, certain chemicals (e.g. phenol, aniline, certain pesticides) can penetrate intact skin and so become absorbed into the body. This may occur through local contamination, e.g. from a liquid splash, or through exposure to high vapour concentrations. Special precautions to avoid skin contact are required with these chemicals and potential exposure via skin absorption has to be taken into account when assessing the adequacy of control measures. Chemicals able to penetrate intact skin are listed in Table 4.2. 

Pesticides may enter the atmosphere during spray applications of the formulated product, by volatilization, through management practices, via wind-distributed soil particles containing absorbed pesticides, etc. Several analytical methods have been reported over the last 30 years for the determination of pesticides in air, and all involve the passage of known volumes of air for a pre-defined time period through an adsorbent material to trap the desired analytes. These analytes are then extracted, concentrated, and analyzed. A few analytical methods have been reported for the determination of triazine compounds in air in the last decade. 

SFE of fruits and vegetables and meat products has been reported, but the sample preparation techniques necessary to obtain reproducible results are extremely time consuming. Solid absorbents such as Hydromatrix, Extrelut " anhydrous magnesium sulfate or absorbent polymers are required to control the level of water in the sample for the extraction of the nonpolar pesticides. Without the addition of Hydromatrix, nonpolar pesticides cannot penetrate the water barrier between the sample particles and the supercritical CO2. The sample is normally frozen and the addition of dry-ice may be required to reduce losses due to degradation and/or evaporation. Thorough reviews of the advantages and limitations of SFE in pesticide residues... 

Obana et alP reported a modified ethyl acetate extraction which used a super absorbent polymer instead of sodium sulfate to absorb water. Eollowing cleanup by carbon-based SPE and/or gel permeation chromatography (GPC), recoveries in excess of 70% were achieved for the majority of the 107 pesticides of interest in asparagus, orange, potato and strawberry. The super absorbent polymers are now being incorporated into ASE procedures. 

A variety of formats and options for different types of applications are possible in CE, such as micellar electrokinetic chromatography (MEKC), isotachophoresis (ITP), and capillary gel electrophoresis (CGE). The main applications for CE concern biochemical applications, but CE can also be useful in pesticide methods. The main problem with CE for residue analysis of small molecules has been the low sensitivity of detection in the narrow capillary used in the separation. With the development of extended detection pathlengths and special optics, absorbance detection can give reasonably low detection limits in clean samples. However, complex samples can be very difficult to analyze using capillary electrophoresis/ultraviolet detection (CE/UV). CE with laser-induced fluorescence detection can provide an extraordinarily low LOQ, but the analytes must be fluorescent with excitation peaks at common laser wavelengths for this approach to work. Derivatization of the analytes with appropriate fluorescent labels may be possible, as is done in biochemical applications, but pesticide analysis has not been such an important application to utilize such an approach. 

The development of solid-phase extraction (SPE) absorbents such as silica gel, alumina and Florisil tremendously aided in the purification or cleanup of pesticide residues from water. 

Calculation of ID using biological monitoring techniques requires the knowledge of the pharmacokinetics of the parent pesticide in laboratory animals. This will allow the use of the parent or its urine metabolite(s) to calculate the total amount of the parent that had been absorbed through the skin of the test subject. The amount of the residue in the urine should be corrected for any molecular weight differences between the parent and its urine metabolite(s) and also corrected for daily urine excretion volumes based on creatinine analysis of the urine samples. 

Irrigation return flows. When farmers irrigate agricultural land, water not absorbed into the ground can flow into reservoirs for reuse. This return flow often picks up pesticide or fertilizer constituents, potentially rendering it hazardous. Because this water may be reused on the fields, it is excluded from the definition of solid waste. 

FCS0 is a lethal (fatal) concentration causing death in 50% of laboratory animals when the pesticide is absorbed through the respiratory tract (inhalation) as a steam or aerosol. 

When humans contact a chemical residue such as a pesticide on a treated surface, some of the deposit can be dislodged or transferred to skin or clothing. Ultimately, a portion of the amount transferred may be absorbed and constitute the absorbed daily dose (ADD). The ADD provides the most precise estimate of exposure that can be practically obtained for humans and has become the most useful expression of exposure for risk assessment and risk management. 

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