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Toxic combustion products from pesticide fires. Executive summary
In order to obtain reliable data on the generation of toxic combustion products and to get more insight into the risks of fires in pesticide warehouses TNO performed the research project 'Toxic combustion products from pesticide fires'. The following research activities have been performed during the project: — A study of the casuistry of pesticide fires; — A literature study of small scale combustion test methods; — Execution of medium scale combustion experiments with pesticides; — A study on the extrapolation of the emissions of small and medium scale combustion tests to real fire conditions; — A study on the prevention and control of fires in pesticide storages. Most important results and conclusions of the project. — The medium scale combustion experiments with parathion, chlorfenvinphos, dichlobenil and 2,4-D indicate the following: — Emissions of solids (particles and soot), carbon monoxide and hydrocarbons are higher than assumed in present hazard assessment studies; - Emissions of nitrogen oxides and chlorinated dioxins and furans are lower than assumed in present hazard assessment studies; - Chlorine and sulphur in the pesticide are nearly fully converted into hydrogen chloride and sulphur dioxide; - The emissions of ammonia, chlorine and phosgene are below or just above detection limits; - Large quantities of solid residues remain in all fires. The residues contain up to 10% unburnt pesticide; - Simulated fire extinguishing or oxygen deficiency do not significantly influence the emissions during the medium scale experiments. — Similarity requirements to extrapolate the emissions to pesticides other than those investigated have been determined. As these similarity requirements will not be completely fulfilled in many cases the uncertainties in the extrapolated emissions are large. — The conservative conversion rates are proposed for a pesticide fire. Fire protection systems — A methodology has been developed to define the required fire protection level of a pesticide storage: - The required fire protection level for a pesticide storage depends on the product fire hazard, the packaging fire hazard, and the environmental and health hazard of the stored materials; - Four fire protection levels for a pesticide storage are distinguished in the methodology, with fire protection levels having different requirements. For level one only the basic minimum requirements like good facility lay out, ignition source control, good housekeeping and regular training of employees are necessary. The highest protection level is level four. For level four automatic fire alarms, sprinkler systems and a basin for extinguishing water are additional requirements. — Application of this methodology is recommended to obtain a cost effective protection level for a pesticide storage taking into account the hazards of the stored pesticides. Small scale test methods — Based on the results of the study on the characteristics of small scale test methods it can be concluded that the applicability of small scale test methods to predict the emission of toxic products of a pesticide fire is very limited. — Small scale methods should be further developed in order to improve the simulation of the fire conditions observed during the medium scale experiments. Case histories — Due to the very general description of the case histories it was impossible to get reliable data on the causes, development and consequences of pesticide fires.
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[Abstract]
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Covalent binding of organophosphorothioates to albumin: A new perspective for OP-pesticide biomonitoring?
We here report on the covalent binding of various organophosphorothioate (OPT) pesticides to albumin at in vitro exposure levels that did not give rise to butyrylcholinesterase inhibition. Adduct formation occurred at the Tyr-411 residue of albumin, as was firmly corroborated by LC-tandem MS analysis of a pepsin digest of OPT-modified albumin. It cannot be excluded that other (tyrosine) residues become modified as well. A convenient method for mass spectrometric determination of the OPT tyrosine adduct has also been developed based on the pronase digestion of albumin and subsequent LC-tandem MS analysis of the digest. The resulting tyrosine phosphorothioate ester displayed favorable chromatographic and mass spectrometric properties for sensitive analysis. In vitro exposure levels of parathion and chlorpyrifos down to 1 μM could readily be assessed. The remarkable affinity of OPTs for albumin opens the way for a more complete assessment of OP pesticide exposure. © 2009 Springer-Verlag.
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[Abstract]
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Half-lives of pesticides on greenhouse crops
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New risk indicator approach for Operators, Workers, Bystanders and Residents for a sustainable use of plant protection products
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2015
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Author: |
Sacchettini, G.
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Calliera, M.
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Marchis, A.
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Glass, R.
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Ellis, C.B.
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Machera, K.
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Gerritsen-Ebben, R.
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Spanoghe, P.
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Capri, E.
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Keywords: |
Nutrition · Sustainable Use Directive · Indirect risk indicators · Pesticide use · Risk reduction · Risk analysis · Pesticide exposure · Food and Nutrition · Healthy Living · Life · RAPID - Risk Analysis for Products in Development · ELSS - Earth, Life and Social Sciences
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In 2009, the European Union adopted the Directive on Sustainable Use of pesticides (SUD, Directive 2009/128/EC) establishing a framework for achieving a sustainable use of Plant Protection Products (PPPs) through reducing the risks and impacts of PPP use on human health and the environment, promoting integrated pest management and stimulating effective non-chemical alternatives. The core idea of the SUD is that it is necessary to monitor the use of PPPs through the implementation of an appropriate set of risk indicators to monitor progress and trends in risk reduction within the Member States. To contribute to this direction, following a comprehensive analysis of the risk (including procedures of risk assessment and risk management) and involving stakeholders in the decision process, specific toolboxes of practical indirect risk indicators of exposure of Operators, Workers, Bystanders and Residents were developed and are now available to be used by Member States (MSs) based on their specific context. © 2015, Springer-Verlag Berlin Heidelberg.
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[Abstract]
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Agricultural pesticide exposure data bases for risk assessment
Chemicals/CAS: Pesticides
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[Abstract]
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Pesticides and other chemical residues in Dutch total diet samples (June 1976-July 1978)
Over a period of 2 yr 126 different food items of a market basket of 16-18 yr old males were purchased every 2 months. The foodstuffs were prepared as for eating, and were combined in 12 commodity groups. Twelves samples of each food group were homogenized and analysed for 78 different chemicals, including pesticides, PCBs, bromine, heavy metals, arsenic and selenium. Thirty-four of these chemicals were detected in the various samples and the means and ranges of residue concentrations found in each food group are reported. Most chemicals were found in concentrations below the Dutch residue tolerance limits, the two exceptions were omethoate and carbendazim. Using the concentrations found in the total diet samples the daily intakes of the various chemicals were calculated. The daily intake figures were evaluated with the aid of the Acceptable Daily Intakes (ADI) recommended by FAO/WHO. For practically all chemicals examined the mean and the maximum intakes were well below the ADI. Chemicals/CAS: arsenic, 7440-38-2; bromine, 7726-95-6; selenium, 7782-49-2; Pesticide Residues
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[Abstract]
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The accuracy of DERM may be a self-fulfilling DREAM
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Controlling persistent organic pollutants-what next?
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1998
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Author: |
Vallack, H.W.
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Bakker, D.J.
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Brandt, I.
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Broström-Lundén, E.
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Brouwer, A.
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Bull, K.R.
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Gough, C.
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Guardans, R.
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Holoubek, I.
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Jansson, B.
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Koch, R.
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Kuylenstierna, J.
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Lecloux, A.
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Mackay, D.
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McCutcheon, P.
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Mocarelli, P.
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Taalman, R.D.F.
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Weavers, N.G.
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Keywords: |
Environment · Bioaccumulation · Biomagnification · Carcinogenicity · Chronic toxicity · Endocrine disruption · Global distillation · Immunotoxicity · Monitoring · Persistence · Persistent organic pollutants · Risk assessment · Chlorinated hydrocarbon · Dioxin · Organic compound · Organochlorine pesticide · Pesticide · Pesticide residue · Polychlorinated dibenzodioxin · Polychlorinated dibenzofuran · Polycyclic aromatic hydrocarbon · Bioaccumulation · Carcinogenicity · Environmental exposure · Cnvironmental monitoring · Environmental protection · Human · Immunotoxicity · Pollution control · Pollution transport · Priority journal · Review · Risk assessment
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Within the context of current international initiatives on the control of persistent organic pollutants (POPs), an overview is given of the scientific knowledge relating to POP sources, emissions, transport, fate and effects. At the regional scale, improvements in mass balance models for well-characterised POPs are resulting in an ability to estimate their environmental concentrations with sufficient accuracy to be of help for some regulatory purposes. The relevance of the parameters used to define POPs within these international initiatives is considered with an emphasis on mechanisms for adding new substances to the initial lists. A tiered approach is proposed for screening the large number of untested chemical substances according to their long-range transport potential, persistence and bioaccumulative potential prior to more detailed risk assessments. The importance of testing candidate POPs for chronic toxicity (i.e. for immunotoxicity, endocrine disruption and carcinogenicity) is emphasised as is a need for the further development of relevant SAR (structure activity relationship) models and in vitro and in vivo tests for these effects. Where there is a high level of uncertainty at the risk assessment stage, decision-makers may have to rely on expert judgement and weight-of-evidence, taking into account the precautionary principle and the views of relevant stake-holders. Close co-operation between the various international initiatives on POPs will be required to ensure that assessment criteria and procedures are as compatible as possible. Copyright (C) 1998 Elsevier Science B.V.
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[Abstract]
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Volatilization of the pesticides chlorpyrifos and fenpropimorph from a potato crop
Volatilization of pesticides from crops in the field can be an important emission pathway. In a field experiment with characterization of meteorological conditions, the pesticides chlorpyrifos and fenpropimorph were sprayed onto a potato crop, after which concentrations in the air and on/in the plants were measured. Rates of volatilization were estimated with the aerodynamic profile (ADP), energy balance (EB), relaxed eddy accumulation (REA), and plume dispersion (PD) methods. The volatilization rates obtained with the ADP and EB methods were similar, while some rates obtained with the REA and PD methods in the initial period were lower. Cumulative volatilization of chlorpyrifos during daylight hours (ADP and EB methods) was estimated to be about 65% of the dosage. By far the majority of this volatilization occurred in the first few days. Competing processes at the plant surface had a considerable effect on the dissipation of fenpropimorph, so cumulative volatilization during daylight hours was estimated to be only 7% of the dosage. Plant surface residues were higher than would correspond with the volatilization rate, indicating that penetration into the leaves had occurred. © 2006 American Chemical Society.
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[Abstract]
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Perceptions of pesticides exposure risks by operators, workers, residents and bystanders in Greece, Italy and the UK
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2015
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Author: |
Remoundou, K.
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Brennana, M.
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Sacchettini, G.
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Panzone, L.
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Butler-Ellis, M.C.
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Capri, E.
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Charistou, A.
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Chaideftou, E.
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Gerritsen-Ebben, M.G.
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Machera, K.
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Spanoghe, P
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Glass, R.
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Marchis, A.
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Doanngoc, K.
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Hart, A.
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Frewer, L.J.
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Keywords: |
Workplace · Pesticide · Exposure · Stakeholder · Perception · Agriculture · Risk · Work and Employment · Healthy Living · Life · RAPID - Risk Assessment Products in Development · ELSS - Earth, Life and Social Sciences
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The EU Directive on the sustainable use of pesticides (EU128/2009/EC) requires European Member States to develop training activities targeting occupational exposure to pesticides, and communication material aimed at residents and bystanders. Risk perceptions, knowledge and attitudes associated with passive and occupational exposure to pesticide potentially influence the extent to which different stakeholders adopt self-protective behaviour. A methodology for assessing the link between attitudes, adoption of self-protective behaviours and exposure was developed and tested. A survey was implemented in the Greece, Italy and the UK, and targeted stakeholders associated with pesticide exposure linked to orchards, greenhouse crops and arable crops respectively. The results indicated that the adoption of protective measures is low for residents and bystanders, with the exception of residents in Greece, when compared to operators andworkers, who tend to followrecommended safety practices. A regression analysis was used to examine the factors affecting the probability of adopting protectivemeasures aswell the as the level of exposure in the case of operators andworkerswhere data are available. The results indicate that the likelihood of engaging in self-protective behaviour is not significantly affected by perceptions of own health being affected by pesticides for residents and bystanders. However, operators who perceive that their heath has been negatively affected by the use of pesticides are found to bemore likely to adopt self-protective behaviours. Gender and country differences, in perceptions, attitudes and self-protection are also observed. Recommendations for improved communication, in particular for vulnerable groups, are provided.
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[Abstract]
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Ecological risk assessment of substances with suspected estrogenic activity using standard laboratory fish tests
The assessment of risks to the aquatic environment in the European Union is generally based on a comparison of Predicted Environmental Concentrations (PEC) with Predicted No Effect Concentrations (PNEC) for surrogate, or `representative', organisms of the receiving waters. Such risk assessments are required for new and priority existing chemicals, pesticides and, in the near future, biocides; they are dependent on robust in vivo test data. Current strategies for ecological risk assessment were not designed to assess the risk of endocrine disrupters. The selection of suitable fish species and practical in vivo end points for determining endocrine disruption in fish are discussed, including the adaptation of some existing guidelines. This paper is partly based on a series of experiments conducted our laboratory to look at the effects of a model alkylphenol (4-tert-pentylphenol), an industrial chemical intermediate, acting as a pseudo-estrogen on an all-male population of the common carp, Cyprinus carpio. Exposure to the test substance occurred at critical life stages for endocrine disruption. Biochemical parameters as well as histological parameters were applied, and their suitability to be used in ecological risk assessment is discussed.
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[Abstract]
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Environmentalist: Introduction
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Implementing atmospheric fate in regulatory risk assessment of pesticides: (How) can it be done?
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1999
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Author: |
Bakker, D.J.
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Gilbert, A.J.
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Gottschild, D.
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Kuchnicki, T.
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Laane, R.W.P.M.
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Linders, J.B.H.J.
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Meent, D. van de
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Montforts, M.H.M.M.
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Pino, J.
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Pol, J.W.
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Straalen, N.M. van
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Keywords: |
Geosciences · Atmospheric fate · Pesticides · Risk assessment · Tiered approach · Air pollution · Ecosystems · Environmental impact · Environmental protection · Risk assessment · Toxicity · Atmospheric fate assessment · Pesticide effects
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Atmospheric fate of pesticides and their possible effects in ecosystems beyond the immediate surrounding of the application site are not actively considered in currently used regulatory, risk assessment schemes. Concern with respect to atmospheric transport and subsequent deposition of pesticides in non-target areas is however growing. In this article the results of discussions on the possibilities of implementing atmospheric fate in regulatory risk assessment are presented. It is concluded that implementing atmospheric fate in regulatory risk assessment schemes is possible and that, from a scientific point of view, these schemes should distinguish between pesticides on the basis of both their possibility/probability to reach non- target areas and on their toxicity. This implies that application of the precautionary principle or use of intrinsic pesticide properties alone is not considered justifiable. It is recommended that the risk assessment scheme should follow a tiered approach. The first tier should be entered only if the existing regulatory risk assessment procedure, including a local PEC:PNEC calculation, has been passed and involves a test for the pesticide's total atmospheric emission potential, i.e. its potential for becoming airborne during and after application. The second tier, which is only entered if the total emission potential is higher than a certain trigger value, should consist of a PEC:PNEC calculation for regional off-site areas (10-50 km) (tier 2A). If the pesticide's atmospheric transport potential is expected to exceed a certain value, the PEC:PNEC ratio should also be calculated for more remote areas (>1000 km) (tier 2B).
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[Abstract]
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Residues of pentachloronitrobenzene and related compounds in greenhouse soils
Pentachloronitrobenzene (PCNB, also known as Quintozene, Terraclor) is used as a soil fungicide in greenhouses, mainly for the control of Rhizoctonia and Botrytis in lettuce. During an examination (by gas liquid chromatography) of a number of soil samples from greenhouses, not only a PCNB peak was found in the chromatograms, but also several other peaks, which were thought to be related to that compound. The identity of these peaks was investigated by mass spectrometry. The results of this study are described. Chemicals/CAS: Aniline Compounds; Anisoles; Benzene Derivatives; Chlorine, 7782-50-5; Hexachlorophene, 70-30-4; Nitrobenzenes; Pesticide Residues
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[Abstract]
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Reliability of concentrations of organophosphate pesticide metabolites in serial urine specimens from pregnancy in the Generation R Study
The widespread use of organophosphate (OP) pesticides has resulted in ubiquitous exposure in humans, primarily through their diet. Exposure to OP pesticides may have adverse health effects, including neurobehavioral deficits in children. The optimal design of new studies requires data on the reliability of urinary measures of exposure. In the present study, urinary concentrations of six dialkyl phosphate (DAP) metabolites, the main urinary metabolites of OP pesticides, were determined in 120 pregnant women participating in the Generation R Study in Rotterdam. Intra-class correlation coefficients (ICCs) across serial urine specimens taken at o18, 18–25, and 425 weeks of pregnancy were determined to assess reliability. Geometric mean total DAP metabolite concentrations were 229 (GSD 2.2), 240 (GSD 2.1), and 224 (GSD 2.2) nmol/g creatinine across the three periods of gestation. Metabolite concentrations from the serial urine specimens in general correlated moderately. The ICCs for the six DAP metabolites ranged from 0.14 to 0.38 (0.30 for total DAPs), indicating weak to moderate reliability. Although the DAP metabolite levels observed in this study are slightly higher and slightly more correlated than in previous studies, the low to moderate reliability indicates a high degree of within-person variability, which presents challenges for designing well-powered epidemiological studies.
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[Abstract]
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16 |
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Pesticides and the residential bystander
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Personal protective equipment for registration purposes of pesticides
Regulatory authorities in North America, Europe and Australia use different approaches for the estimation of exposure reduction effectiveness of personal protective equipment (PPE) in registration processes of agrochemical pesticides. TNO has investigated current views and facts for the use of default values and set up a discussion paper which can be used as a starting point to achieve an internationally harmonised set of PPE protection factors for regulatory use. For inhalation exposure Loading it is proposed to use the assigned protection factors (APF) as deduced by BSI (British Standard Institution) and ANSI (American National Standards Institution). Since these values are somewhat variance and since in agricultural settings efficient control and proper training and education with respect to inhalation protection devices is generally absent, it is good to err on the safe side and to use the Lowest of both values, if available. For dermal exposure Loading differentiations are made for operators and re-entry workers and further for hand and body protection. Next to this the restrictions and framework for the use of the proposed defaults are very relevant. Oral exposure loading is only considered in special cases where dermal exposure may be relatively high and the hand-mouth shunt may lead to appreciable oral exposure loading. The presented defaults for PPE have been discussed with experts of regulatory authorities and industry, but a formal discussion still has to take place. This needs to be done on EU level between Member States. The current proposal is based on state-of-the-art knowledge and policy considerations, but further research is needed to better underpin the proposed values and/or to adapt them.
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[Abstract]
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18 |
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Transformations of pesticides in the atmosphere : A state of the art
The current knowledge about transformation rates and products of pesticides in the atmosphere is reviewed. Reactive species and their concentrations in the atmosphere are presented. Reactions of pesticides with these species (including photolysis) in the gas and the particulate phase are evaluated from available experimental data. The potential of estimation methods is discussed. Experimental techniques for laboratory and outdoor measurements are reviewed. Finally, an estimation is made of uncertainties in atmospheric lifetimes due to chemical or physical reactions. It is concluded that the most important transformation of pesticides in the atmosphere is due to reaction with OH radicals. Very few experimental data for pesticides are available though. The levels of uncertainty in OH radical concentrations are acceptable, however, for a proper estimation of atmospheric removal rates due to reactions with OH radicals of those pesticides for which experimental transformation rates (of homologues) are available.
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[Abstract]
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Gas chromatographic determination of acid herbicides in surface water samples with electron-capture detection and mass spectrometric confirmation
The development of a multi-residue method for the determination of eight polar acidic herbicides (MCPA, MCPB, mecoprop, 2,4-D, dichlorprop, bentazone, dicamba and dikegulac) in surface water is described. The method involves an off-line solid-phase extraction (SPE) procedure prior to instrumental analysis. The herbicides are isolated on an SPE C,, column and derivatized with pentafluorobenzyl bromide. After clean-up of the obtained solution on a disposable silica gel cartridge, the herbicide derivatives are determined by capillary gas chromatography with electron-capture detection and confirmed by capillary gas chromatography with mass selective detection using negative chemical ionization. The detection limits for the herbicides are in the range of 0.02-0.05 μg per litre surface water. The average recovery is 93%. A few hundreds of water samples were successfully analysed with this method.
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[Abstract]
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20 |
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Transfer of chemicals from feed to animal products: The use of transfer factors in risk assessment
The human risk assessment of feed contaminants has often been hampered by a lack of knowledge concerning their behaviour when consumed by livestock. To gain a better understanding of the transfer of contaminants from animal feed to animal products, a meta-analysis of public literature was made. Data concerning feed contaminant concentrations, feeding periods, residue levels in animal products, and other parameters were gathered and recorded. For each case a 'transfer factor', which was defined as the ratio of the concentration of a chemical in an animal product to the concentration of the chemical in animal feed, was calculated. Scientifically founded transfer factors were calculated and analysed for groups of chemicals based on their contaminant classes or physicochemical properties. These database-derived transfer factors enable a more accurate risk assessment in the case of a feed contamination, and enable rapid risk management decision-making and/or intervention.
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[Abstract]
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