The use of 6Li{7Li}-REDOR NMR spectroscopy to compare the ionic conductivities of solid-state lithium ion electrolytes.

Garnet-like solid-state electrolyte materials for lithium ion batteries are promising replacements for the currently-used liquid electrolytes. This work compares the temperature dependent Li(+) ion hopping rate in Li6BaLa2M2O12 (M = Ta, Nb) using solid-state (6)Li{(7)Li}-REDOR NMR. The slope of the (6)Li{(7)Li}-REDOR curve is highly temperature dependent in these two phases, and a comparison of the changes of the REDOR slopes as a function of temperature has been used to evaluate the Li(+) ion dynamics. Our results indicate that the Nb phase has a higher overall ionic conductivity in the range of 247 K to 350 K, as well as a higher activation energy for lithium ion hopping than the Ta counterpart. For appropriate relative timescales of the dipolar couplings and ion transport processes, this is shown to be a facile method to compare ion dynamics among similar structures.

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.

An assessment of dermal exposure to semi-synthetic metal working fluids by different methods to group workers for an epidemiological study on dermatitis.

BACKGROUND: Assessment of exposure assessment to metal working fluids (MWF) has almost exclusively focused on inhalation exposure. AIMS: To assess levels of, and factors affecting, dermal and inhalation exposure to semi-synthetic MWF, and to identify suitable dermal exposure grouping schemes among metal workers for an epidemiological survey on dermatitis of hands, forearms, and head. METHODS: A cross-sectional survey was conducted in four metal working machining departments of a truck manufacturing plant, estimating dermal and inhalation exposure levels to semi-synthetic metal working fluids (SMWF) in machine operators. Dermal exposure levels to SMWF were estimated by three different methods for dermal exposure assessment (VITAE, surrogate skin pad method, and a semi-quantitative dermal exposure assessment method (DREAM)). RESULTS: The identified factors affecting dermal exposure were similar for the three methods, although differences were found for estimated variability in dermal exposure levels between groups, within groups (among workers), and from day to day. With the VITAE method differences in exposure levels were detected between workers that were not detected with the surrogate skin pad method, and only partly with the DREAM method. CONCLUSIONS: Considering the additional effort and costs that use of the VITAE method entailed, the observational semi-quantitative DREAM method appeared to be more efficient for grouping of dermal exposure levels for the epidemiological study on dermatitis.

Determinants of dermal exposure relevant for exposure modelling in regulatory risk assessment.

Risk assessment of chemicals requires assessment of the exposure levels of workers. In the absence of adequate specific measured data, models are often used to estimate exposure levels. For dermal exposure only a few models exist, which are not validated externally. In the scope of a large European research programme, an analysis of potential dermal exposure determinants was made based on the available studies and models and on the expert judgement of the authors of this publication. Only a few potential determinants appear to have been studied in depth. Several studies have included clusters of determinants into vaguely defined parameters, such as 'task' or 'cleaning and maintenance of clothing'. Other studies include several highly correlated parameters, such as 'amount of product handled', 'duration of task' and 'area treated', and separation of these parameters to study their individual influence is not possible. However, based on the available information, a number of determinants could clearly be defined as proven or highly plausible determinants of dermal exposure in one or more exposure situation. This information was combined with expert judgement on the scientific plausibility of the influence of parameters that have not been extensively studied and on the possibilities to gather relevant information during a risk assessment process. The result of this effort is a list of determinants relevant for dermal exposure models in the scope of regulatory risk assessment. The determinants have been divided into the major categories 'substance and product characteristics', 'task done by the worker', 'process technique and equipment', 'exposure control measures', 'worker characteristics and habits' and 'area and situation'. To account for the complex nature of the dermal exposure processes, a further subdivision was made into the three major processes 'direct contact', 'surface contact' and 'deposition'.

Proposal for an approach with default values for the protection offered by PPE, under European new or existing substance regulations.

Introduction of personal protective equipment (PPE) in the process of quantitative exposure and risk assessment should be addressed carefully. PPE which have been designed and manufactured according to CE-criteria and have proved to pass relevant test criteria, can be classified as "proper functioning". However, test criteria for PPE are not equal to levels of protection which can be achieved in the workplace, because actual workplace exposure scenarios, fit, maintenance and storage may differ substantially from the test conditions. The proper use of PPE is related to issues which form a part of a PPE-programme. Such a programme should be implemented in a company to ensure selection of proper PPE and information, training and instruction of employees how to wear PPE properly. Assigned protection factors (APFs) for different designs of respiratory protective devices (RPD) have been introduced to quantify effectiveness of RPD in the workplace. Similar APFs are proposed for dermal protection (gloves and clothing). In general biological monitoring studies show lower reduction of internal exposure than estimated by reduction of external exposure. Therefore, conservative estimates of protection by PPE, i.e. the lowest APFs, are proposed for risk assessment purposes if "proper use of proper functioning" PPE as part of a PPE-programme cannot be demonstrated.

A dermal model for spray painters. Part I: subjective exposure modelling of spray paint deposition.

The discriminative power of existing dermal exposure models is limited. Most models only allow occupational hygienists to rank workers between and within workplaces according to broad bands of dermal exposure. No allowance is made for the work practices of different individuals. In this study a process-based, structured approach has been used to estimate dermal exposure from overspray generated by a spray painting process. Factors for spray technique, object shape and workers' individual work practices involved in the processes of droplet formation and deposition were incorporated into the model. The model was applied to predict dermal exposure of airless spray painters and the results were compared with exposure data. The predicted levels of exposure showed reasonable rank correlation with the measured exposure, although the model tended to over-predict the actual level of exposure. It was concluded that a structured, process-based approach has the potential to produce reliable estimates of dermal exposure. The reliability of exposure models of this type should be explored further and the relationship between the determinants of exposure should be validated by additional field studies.

A dermal model for spray painters. Part II: estimating the deposition and uptake of solvents.

The contribution of dermal exposure to the total body burden of a given chemical is difficult to assess. However, it is possible that as regulatory pressures lead to reductions in inhalation exposure, the proportion of uptake via the dermal route will increase. This study brings together recent work in the field of dermal exposure to provide a model to estimate both exposure and uptake of solvents through the skin. Using spray painters as an example, the process of modelling exposure is described from identifying the determinants of exposure through to calculating the flux of solvent through the stratum corneum and thus the total dermal uptake. Results from a range of exposure scenarios are presented and areas requiring further research and validation are highlighted. The model should allow the estimation of combined dermal and inhalation exposure to solvents in both current work situations and retrospective epidemiological studies. Furthermore, it is envisaged that the model may provide the basis for generic assessment of dermal exposure and uptake.

Hand wash and manual skin wipes.

Hand wash and skin wipes are major techniques that have been used for dermal exposure sampling. Both techniques remove chemicals either deposited on or transferred to the skin contaminant layer by a combination of chemical and mechanical actions. The paper overviews identified methods and techniques, with emphasis on sampling parameters and sampling efficiency. It is concluded that identified sampling protocols, including sampling techniques, deviate at possible key issues, which hampers comparisons of study results. It is recommended to conduct sampling efficiency studies prior to field sampling, under conditions that are quite similar to conditions of exposure regarding exposure process, levels of skin loading, and time of residence of the compound on the skin. Harmonization of sampling protocols will be a first step in creating a database for better understanding the influence of sampling parameters on the performance of removal techniques to assess dermal exposure.

Use of qualitative and quantitative fluorescence techniques to assess dermal exposure.

Fluorescent tracers provide a way of simultaneously assessing the mass of a contaminant hazardous substance on the surface of the skin of a worker and the area of skin exposed. These parameters, along with the duration of exposure and the estimated contaminant concentration in the skin contamination layer, can be used to calculate the likely uptake through the skin. Repeated assessment of the mass of tracer on a surface within a room or on the surface of the skin can also allow the net transfer of contaminant to that compartment to be estimated. Qualitative evaluation of transfer processes using fluorescent tracers can help identify important secondary sources of exposure.

Assessment of dermal exposure during airless spray painting using a quantitative visualisation technique.

The range of dermal exposure to non-volatile compounds during spray painting was studied in a semi-experimental study involving three enterprises and 12 painters. A fluorescent tracer was added to the paint and deposition of the tracer on clothing and uncovered parts of the skin was assessed using video imaging and processing techniques. A container (volume 36 m(3)) was sprayed with a colourless laquer (varnish) containing 66.7 mg/l fluorescent whitening agent. All painters sprayed the outside of the container. Nine painters repeated the painting a second time and five also sprayed the inside of the container. The painters wore white Tyvek coveralls, but no gloves. Duration of spraying the outside ranged from 4 to 21 min with a mean of 10 min and the amount of paint sprayed ranged from 3.0 to 12.8 l (mean 6.6 l). The mass of tracer deposited on the coverall ranged from 2.2 to 471 microg (90th percentile 256 microg), whereas, mass deposited on skin (i.e. the hands, wrists, and face) ranged from 0.01 to 52 microg tracer (90th percentile 20 microg). The quantity of tracer on the coverall was three times higher after spraying the inside of the container compared to spraying the outside, whereas the quantity on the skin was similar in both cases. On average 10% of the surface area of the coverall and skin was exposed during spraying the outside. Exposures, expressed in units of mass per area exposed were slightly higher for skin compared to coverall. In this study, deposited mass of tracer was correlated with an alternative exposure metric, i.e. surface area exposed multiplied by the duration of exposure, which has been proposed as a surrogate for uptake. Using a quantitative fluorescent tracer technique, it could be demonstrated that body parts which showed the lowest mass of tracer had the highest exposure as mass per surface area. Compared to other techniques which only determine mass, the ability to identify and quantify the actual surface area exposed is a clear advantage of the quantitative fluorescent tracer technique.

Transfer of contaminants from surface to hands: experimental assessment of linearity of the exposure process, adherence to the skin, and area exposed during fixed pressure and repeated contact with surfaces contaminated with a powder.

Estimation of dermal exposure in the workplace resulting from contact with contaminated surfaces is important in risk assessment. Models have been developed to describe the process of exposure due to transfer, but for major input parameters--that is, contact area surface and adherence--defaults are used. This study examines the effect of one single-hand press contact and repeated contacts with a contaminated glass plate on both skin area exposed and loading of the skin for three volunteers. A fluorescent whitening agent was used to study the process of exposure and to determine the increase of the area exposed as well as the adherence of the compound to the skin surface after 1 to 12 consecutive contacts by a video imaging technique. In addition, loading of the skin after 12 contacts was compared to loading of a cotton glove monitor with similar hand pressures. The results show that after one single-hand contact only 4 to 16 percent of the total surface of the palm of the hand was exposed, whereas after 12 contacts this was increased to about 40 percent. The efficiency of transfer was < or = 2 percent of the contamination of the surface. The adherence to the skin was 1.07 micrograms/cm2 after 12 contacts and tended to increase non-linearly with increase in contacts. Because defaults of adherence for use in exposure models are generally a factor 500 to 5,000 higher, and the area exposed is assumed to be the total surface of the hand, overestimation of dermal exposure due to a single hand-surface contact in workplaces may occur. Therefore, additional studies on multi-contact exposure scenarios are indicated to adjust defaults for hand-surface transfer processes.

Conceptual model for assessment of dermal exposure.

Dermal exposure, primarily to pesticides, has been measured for almost half a century. Compared with exposure by inhalation, limited progress has been made towards standardisation of methods of measurement and development of biologically relevant exposure measures. It is suggested that the absence of a consistent terminology and a theoretical model has been an important cause of this lack of progress. Therefore, a consistent terminology based on a multicompartment model for assessment of dermal exposure is proposed that describes the transport of contaminant mass from the source of the hazardous substance to the surface of the skin. Six compartments and two barriers together with eight mass transport processes are described. With the model structure, examples are given of what some existing methods actually measure and where there are limited, or no, methods for measuring the relevant mass in a compartment or transport of mass. The importance of measuring the concentration of contaminant and not mass per area in the skin contaminant layer is stressed, as it is the concentration difference between the skin contamination layer and the perfused tissue that drives uptake. Methods for measuring uptake are currently not available. Measurement of mass, concentration, and the transport processes must be based on a theoretical model. Standardisation of methods of measurement of dermal exposure is strongly recommended.

Implementation and evaluation of the fluorescent tracer technique in greenhouse exposure studies.

Knowledge of the level of exposure is important for health risk estimation and risk management. Recently, the occurrence of dermal exposure in many situations has been recognized and estimated to be relevant for worker health. Dermal exposure measurement techniques are therefore needed and several approaches have been taken to assess this type of exposure. The purpose of the present study was to apply and evaluate the fluorescent tracer technique, being one of the most promising and innovative techniques to estimate dermal exposure. The image acquisition is fully calibrated and validated. The most significant aspects of the image analysis process are validated in laboratory settings. The system is applied in a field study to estimate dermal exposure of operators and harvesters in greenhouses, while chemical analysis of clothing exposure is also performed. For operators, the correlation coefficient between the active substance (propoxur) and the fluorescent compound (Tinopal) was 0.92, and for harvesters 0.85. It is concluded that the variability in the analytical technique used is insignificant with respect to the variability in exposure within and between workers. Instead of improving the measuring technique, one might better lower the variability by measuring, for instance, a larger number of workers and/or by standardizing work procedures. The fluorescent tracer technique, being a fast method to estimate dermal exposure, enables the estimation of larger numbers of individuals. Furthermore, the qualitative use of this technique can lead to a more efficient sampling strategy since the exposed body area to evaluate can easily be visualized and selected.

Exposure and risk estimation for pesticides in high-volume spraying.

During twenty applications with a spray pistol of methomyl to chrysanthemums, inhalation exposure as well as potential and actual dermal exposure were monitored using the 'whole-body'-method. On the basis of the exposure data, in terms of exposure to the liquid formulation and the spray liquid, the possible health risk for methomyl and thirteen other pesticides, frequently used in ornamentals, was indicatively assessed. From the No-Observed-Adverse-Effect-Level (NOAEL) in animal experiments an Indicative Limit Value (ILV) was derived. The ILV is considered indicative for the limit of daily exposure for a worker which probably gives no rise to adverse health effects. This value is a rough approximation since the database for a proper assessment of such a value is generally incomplete. Assuming that exposure is independent of the pesticide, using a suitable format, the actual observed exposure can be compared with the ILV. To reduce the dermal exposure levels below the ILV the exposure of especially the hands has to be reduced e.g. by using impermeable gloves.

Proposal for the assessment of quantitative dermal exposure limits in occupational environments: Part 1. Development of a concept to derive a quantitative dermal occupational exposure limit.

Dermal uptake of chemicals at the workplace may contribute considerably to the total internal exposure and so needs to be regulated. At present only qualitative warning signs--the "skin notations"--are available as instruments. An attempt was made to develop a quantitative dermal occupational exposure limit (DOEL) complementary to respiratory occupational exposure limits (OELs). The DOEL refers to the total dose deposited on the skin during a working shift. Based on available data and experience a theoretical procedure for the assessment of a DOEL was developed. A DOEL was derived for cyclophosphamide and 4,4-methylene dianiline (MDA) according to this procedure. The DOEL for MDA was tested for applicability in an actual occupational exposure scenario. An integrated approach is recommended for situations in which both dermal and respiratory exposures contribute considerably to the internal exposure of the worker. The starting point should be an internal health based occupational exposure limit--that is, the maximum dose to be absorbed without leading to adverse systemic effects. The proposed assessment of an external DOEL is then either based on absorption rate or absorption percentage. The estimation of skin penetration seems to be of crucial importance in this concept. If for a specific substance a maximal absorption rate can be estimated a maximal skin surface area to be exposed can be assessed which may then serve the purpose of a DOEL. As long as the actual skin surface exposed is smaller than this maximal skin surface area the internal OEL will not be exceeded, and therefore, no systemic health problems would be expected, independent of the dermal dose/unit area. If not, the DOEL may be interpreted as the product of dermal dose/unit area (mg/cm2) and exposed skin surface area (cm2). The proposed concept for a DOEL is relevant and can be made applicable for health surveillance in the occupational situation where dermal exposure contributes notably to the systemic exposure. Further research should show whether this concept is more generally applicable.

Proposal for the assessment to quantitative dermal exposure limits in occupational environments: Part 2. Feasibility study for application in an exposure scenario for MDA by two different dermal exposure sampling methods.

OBJECTIVE: To evaluate two different techniques for assessing dermal exposure to 4,4'-methylene dianiline (MDA) in a field study. The results were used to test the applicability of a recently proposed quantitative dermal occupational exposure limit (DOEL) for MDA in a workplace scenario. METHODS: For two consecutive weeks six workers were monitored for exposure to MDA in a factory that made glass fibre reinforced resin pipes. Dermal exposure of the hands and forearms was assessed during week 1 by a surrogate skin technique (cotton monitoring gloves) and during week 2 by a removal technique (hand wash). As well as the dermal exposure sampling, biological monitoring, measurement of MDA excretion in urine over 24 hours, occurred during week 2. Surface contamination of the workplace and equipment was monitored qualitatively by colorimetric wipe samples. RESULTS AND CONCLUSIONS: Geometric means of daily exposure ranged from 81-1762 micrograms MDA for glove monitoring and from 84-1783 micrograms MDA for hand washes. No significant differences, except for one worker, were found between exposure of the hands in weeks 1 and 2. Significant differences between the mean daily exposure of the hands (for both weeks and sampling methods) were found for all workers. The results of the colorimetric wipe samples indicated a general contamination of the workplace and equipment. Excretion of MDA in 24 hour urine samples ranged from 8 to 249 micrograms MDA, whereas cumulative MDA excretion over a week ranged from 82 to 717 micrograms MDA. Cumulative hand wash and MDA excretion results over a week showed a high correlation (R2 = 0.94). The highest actual daily dermal exposure found seemed to be about 4 mg (hand wash worker A on day 4), about 25% of the external DOEL. Testing of compliance by means of a biological limit value (BLV) led to similar results for the same worker. It is concluded that both dermal exposure monitoring methods were applicable and showed a compatible performance in the present exposure scenario, where the exposure relevant to dermal absorption is considered mainly restricted to hands. The concept for a DOEL seemed to be relevant and applicable for compliance testing and health surveillance in the situation under investigation.

The influence of skin moisture on the dermal absorption of propoxur in human volunteers: a consideration for biological monitoring practices.

A large number of workers in agriculture are exposed daily (through skin contact) to pesticides either directly during mixing and loading or indirectly due to contact. The aim of this study was to investigate the influence of skin moisture on the dermal uptake of the pesticide propoxur. The study was conducted in human volunteers under controlled temperature conditions (30 degrees C) and environmental relative humidities of either 50, 70 or 90%. The study was approved by the Medical Ethics Committee. In this study a linear relationship between the environmental relative humidity and the level of skin moisture was observed. The results indicate that the level of skin moisture influences the absorption of propoxur via the dermal route, dramatically ranging from, on average, 13, 33-63% of the potentially absorbed dose' which is excreted in urine as the primary metabolite 2-isopropoxyphenol (IPP) at relative humidity levels of, on average 50, 70 and 90%, respectively. The 'potentially absorbed dose' is defined as the difference between the applied dose and the dislodged dose after 4 h. It can be concluded that by assessing health risks of workers in agriculture exposed dermally to pesticides and e.g. in testing the efficiency of protective clothing under realistic conditions, the influence of the level of skin moisture on absorption of substances may be considerable and has to be taken into account.

Assessment of dermal exposure to chemicals.

The methods for the dermal exposure assessment vary in their complexity and are in some sense complementary to each other. The most easy-to-use methods involve a pseudo-skin-approach, such as gloves and removal by washing. In some cases generic modelling appears to be possible. The experimental methods can indicate and even quantitate the presence of chemicals on the skin. This enables studies on the occurrence of local effects in relation to the exposure. When the interest is on systemic effects, the dermal exposure is only of interest if it represents the amount that is available for penetration through the skin. This may vary largely between compounds due to the large variation in dermal absorption. When this degree of absorption is not known, the alternate method may be biological monitoring, at least when it is based on a detailed pharmacokinetic knowledge of that compound. The most sophisticated method, applied to study occupational exposures, is formed by a combination of monitoring on clothing (pseudo-skin), hand washing (removal) and biological monitoring. In any case, the assessment of dermal exposure should be based on a sampling strategy that takes into account the distribution of the contamination on the body, the variation in time of the exposure, the duration of the exposure as well as the degree of skin protection afforded by clothing.