2,4,6-Trinitrotoluene, TNT, is an explosive used in munitions production that is known to cause both aplastic and hemolytic anemia in exposed workers. Deaths have been reported secondary to both varieties of anemia. Studies have shown that TNT systemic absorption is significant by both the respiratory and dermal routes. A literature review revealed that the most recent review article on TNT exposure arguing for a TWA drop from the PEL to the TLV was in 1977 -- this article cited anemia issues in addition to other untoward effects of TNT. No studies encountered looked at hemoglobin change or anemia cases in respiratory protected workers, this present effort may be the first. TNT PEL (1.5mg/m^3), REL (0.5mg/m^3), and TLV (0.1 mg/m^3) 8 hr TWAs all with skin notations (based on animal models and TNT urine metabolite extrapolation in TNT workers suggesting important role of skin absorption). The earliest effects of systemic TNT poisoning involve hgb and hematocrit drop. The investigator hypothesized that respiratory protection alone is insufficient to protect TNT workers from the risk of anemia development and hemoglobin concentration drop. A retrospective observational study design was incorporated utilizing a records review of TNT vapor air concentration values and worker Hgb values for 8 sets of workers in respiratory protection at a demilitarization operation from October 2006 to April 2007 in order to observe whether or not respiratory protection provided adequate protection against anemia development and hemoglobin change; and to help characterize the probable role of TNT skin absorption on hemoglobin change and anemia risk. Worker baseline hgbs were compared with their exposure hgbs for statistically significant hgb concentration changes (two-tailed paired t-tests), and anemia cases were recorded. Mean hgb changes within each of the 8 groups of workers were then regressed on mean TNT air concentrations (10 hr TWAs) using air sampling levels that were performed closest in time to exposure hgbs. Statistically significant hgb concentration drops and anemia cases were apparent at values about the REL and PEL in respiratory protected workers. There were no anemia cases or statistically significant hgb drops at values about the TLV, however. For mean TNT air concentrations from 0.12/m 3 to 0.31/m 3 there was strong positive linear association with regard to magnitude of hgb change (r=0.996). The results appear to confirm the necessity of the skin notation for TNT. However, the TLV seems to be protective against the possibility of anemia risk principally by the dermal route in workers who are respiratory protected. A question does still remain, however, as to anemia risk in workers who are below the TLV who may not be using respiratory protection. The absence of a continued linear association between mean TNT air concentrations and mean hgb change above the 0.31 mg/m 3 TNT level most likely reflects a marrow response, as the TNT levels evident in the study are reported to be mainly associated with extravascular hemolysis with a minimal, or non-existent, aplastic component assumed. This study adds evidence to the argument that the TLV should be adopted as the new PEL.

Calibration methods for quantitative on-site sampling using solid phase microextraction (SPME) were developed based on diffusion mass transfer theory. This was investigated using adsorptive polydimethylsiloxane/divinylbenzene (PDMS/DVB) and Carboxen/polydimethylsiloxane (CAR/PDMS) SPME fiber coatings with volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene) as test analytes. Parameters that affected the extraction process (sampling time, analyte concentration, water velocity, and temperature) were investigated. Very short sampling times (10-300 s) and sorbents with a strong affinity and large capacity were used to ensure a 'zero sink' effect calibrate process. It was found that mass uptake of analyte changed linearly with concentration. Increase of water velocity increased mass uptake, though the increase is not linear. Temperature did not affect mass uptake significantly under typical field sampling conditions. To further describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross flow was used. An empirical correlation to this model was used to predict the mass transfer coefficient. Findings indicated that the predicted mass uptake compared well with experimental mass uptake. The new model also predicted rapid air sampling accurately. To further integrate the sampling and analysis processes, especially for on-site or <i>in-vivo</i> investigations where the composition of the sample matrix is very complicated and/or agitation of the sample matrix is variable or unknown, a new approach for calibration was developed. This involved the loading internal standards onto the extraction fiber prior to the extraction step. During sampling, the standard partially desorbs into the sample matrix and the rate at which this process occurs, was for calibration. The kinetics of the absorption/desorption was investigated, and the isotropy of the two processes was demonstrated, thus validating this approach for calibration. A modified SPME device was used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. The sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process was shown to be described by Fick's first law of diffusion, whereby the amount of analyte accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. TWA passive sampling with a SPME device was shown to be almost independent of face velocity, and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusional path length could be changed. Environmental conditions (temperature, pressure, relative humidity, and ozone) had little or no effect on sampling rate. When the SPME device was tested in the field and the results compared with those from National Institute of Occupational Health and Safety (NIOSH) method 1501 good agreement was obtained. To facilitate the use of SPME for field sampling, a new field sampler was designed and tested. The sampler was versatile and user-friendly. The SPME fiber can be positioned precisely inside the needle for TWA sampling, or exposed completely outside the needle for rapid sampling. The needle is protected within a shield at all times hereby eliminating the risk of operator injury and fiber damage. A replaceable Teflon cap is used to seal the needle to preserve sample integrity. Factors that affect the preservation of sample integrity (sorbent efficiency, temperature, and sealing materials) were studied. The use of a highly efficient sorbent is recommended as the first choice for the preservation of sample integrity. Teflon was a good material for sealing the fiber needle, had little memory effect, and could be used repeatedly. To address adsorption of high boiling point compounds on fiber needles, several kinds of deactivated needles were evaluated. RSC-2 blue fiber needles were the more effective. A preliminary field sampling investigation demonstrated the validity of the new SPME device for field applications.

Calibration methods for quantitative on-site sampling using solid phase microextraction (SPME) were developed based on diffusion mass transfer theory. This was investigated using adsorptive polydimethylsiloxane/divinylbenzene (PDMS/DVB) and Carboxen/polydimethylsiloxane (CAR/PDMS) SPME fiber coatings with volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene) as test analytes. Parameters that affected the extraction process (sampling time, analyte concentration, water velocity, and temperature) were investigated. Very short sampling times (10-300 s) and sorbents with a strong affinity and large capacity were used to ensure a 'zero sink' effect calibrate process. It was found that mass uptake of analyte changed linearly with concentration. Increase of water velocity increased mass uptake, though the increase is not linear. Temperature did not affect mass uptake significantly under typical field sampling conditions. To further describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross flow was used. An empirical correlation to this model was used to predict the mass transfer coefficient. Findings indicated that the predicted mass uptake compared well with experimental mass uptake. The new model also predicted rapid air sampling accurately. To further integrate the sampling and analysis processes, especially for on-site or <i>in-vivo</i> investigations where the composition of the sample matrix is very complicated and/or agitation of the sample matrix is variable or unknown, a new approach for calibration was developed. This involved the loading internal standards onto the extraction fiber prior to the extraction step. During sampling, the standard partially desorbs into the sample matrix and the rate at which this process occurs, was for calibration. The kinetics of the absorption/desorption was investigated, and the isotropy of the two processes was demonstrated, thus validating this approach for calibration. A modified SPME device was used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. The sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process was shown to be described by Fick's first law of diffusion, whereby the amount of analyte accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. TWA passive sampling with a SPME device was shown to be almost independent of face velocity, and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusional path length could be changed. Environmental conditions (temperature, pressure, relative humidity, and ozone) had little or no effect on sampling rate. When the SPME device was tested in the field and the results compared with those from National Institute of Occupational Health and Safety (NIOSH) method 1501 good agreement was obtained. To facilitate the use of SPME for field sampling, a new field sampler was designed and tested. The sampler was versatile and user-friendly. The SPME fiber can be positioned precisely inside the needle for TWA sampling, or exposed completely outside the needle for rapid sampling. The needle is protected within a shield at all times hereby eliminating the risk of operator injury and fiber damage. A replaceable Teflon cap is used to seal the needle to preserve sample integrity. Factors that affect the preservation of sample integrity (sorbent efficiency, temperature, and sealing materials) were studied. The use of a highly efficient sorbent is recommended as the first choice for the preservation of sample integrity. Teflon was a good material for sealing the fiber needle, had little memory effect, and could be used repeatedly. To address adsorption of high boiling point compounds on fiber needles, several kinds of deactivated needles were evaluated. RSC-2 blue fiber needles were the more effective. A preliminary field sampling investigation demonstrated the validity of the new SPME device for field applications.

Le POCIS (Polar Organic Chemical Integrative Sampler) est un outil d'échantillonnage intégratif alternatif aux techniques d'échantillonnages classiques (ponctuelle ou automatisée) dédié à la mesure de micropolluants organiques relativement hydrophiles dans les eaux. Cet outil permet d'intégrer les concentrations dans le temps (CTWA, Time-Weighted Average Concentration) et, dans certains cas, d'abaisser les limites de quantification. Une revue bibliographique détaillée a montré la forte variabilité des données de performances du POCIS mesurées en laboratoire (notamment les taux d'échantillonnage ou Rs). Cette variabilité résulte en majeure partie de systèmes expérimentaux d'étalonnage différents selon les études et pas toujours renseignés. Dans la littérature, les CTWA obtenues in situ sont comparées aux concentrations obtenues après échantillonnage classique, tel que mis en œuvre actuellement dans les programmes de surveillance européens ; ces concentrations sont dans la plupart des cas du même ordre de grandeur, même si elles ne représentent pas tout à fait la même information. Avec comme objectif d'obtenir des CTWA les plus justes et robustes possibles, nous avons étudié le comportement du POCIS « pharmaceutique » en laboratoire vis-à-vis de 56 micropolluants (hormones, pharmaceutiques, alkylphénols, pesticides, filtre UV), dans un système expérimental d'étalonnage conçu spécifiquement pour contrôler l'ensemble des conditions expérimentales ayant une influence sur les Rs. Nous avons ainsi déterminé 43 Rs robustes et démontré que le POCIS est bien adapté à l'échantillonnage de la plupart des molécules étudiées. De plus, l'allure des cinétiques d'accumulation est expliquée à l'aide des propriétés physico-chimiques des molécules (log D , surface polaire). Cinq homologues deutérés ont été identifiés en tant que PRC (Performance Reference Compounds), c'est-à-dire qu'ils peuvent être utilisés pour corriger les différences de conditions entre le laboratoire et le terrain. Nous avons également comparé le POCIS au Chemcatcher « polaire » en laboratoire et montré qu'en terme de domaine d'application et de performances, le POCIS est mieux adapté pour les micropolluants étudiés. Enfin, nous avons testé la justesse et la robustesse du POCIS lors de deux essais inter-laboratoires (EIL). Le premier EIL, portant sur l'étalonnage de l'outil en laboratoire, a démontré la robustesse de ses performances pour 3 pesticides. Le deuxième EIL in situ a démontré la pertinence du POCIS pour échantillonner des hormones, des pharmaceutiques et des pesticides dans un effluent de station d'épuration. Cette thèse permet d'avancer dans le domaine des connaissances sur l'outil POCIS et de favoriser son application dans le cadre de la directive sur l'eau / The POCIS (Polar Organic Chemical Integrative Sampler) is an alternative integrative sampling tool to conventional sampling methods (grab or automated) for measuring hydrophilic organic micropollutants in water. This tool permits to supply time-weighted average concentrations (TWAC) and, sometimes, to decrease limits of quantification. A detailed bibliographic review showed the important variability of POCIS performance data measured in laboratory (notably the sampling rates or Rs). This variability is in majority due to different experimental calibration systems, not always well detailed, among studies. In the literature, in situ TWAC are compared to concentrations from conventional sampling, actually used in European monitoring programs ; these concentrations are generally of the same order of magnitude, even if they do not represent the same information. In order to obtain accurate and robust TWAC, we studied in laboratory the “pharmaceutical” POCIS behavior for 56 micropollutants (hormones, pharmaceuticals, alkylphenols, pesticides, UV filter), in a calibration system specifically made for controlling the whole experimental conditions having an influence on Rs. We determined 43 robust RS and demonstrated that POCIS is well adapted for sampling most of studied molecules. Moreover, the pattern of kinetic accumulations is explained using molecule physical-chemical properties (log D, polar surface). Five deuterated homologues were identified as PRCs, meaning that they can be used for correcting differences in conditions between the laboratory and the field. We also compared the POCIS with the “polar” Chemcatcher and we showed that in term of application field and performances, the POCIS is better adapted for studied micropollutants. At last, we tested the accuracy and the robustness of the POCIS during two inter-laboratory studies (ILSs). The first ILS, dealing with the laboratory calibration of the tool, demonstrated performance robustness for 3 pesticides. The second in situ ILS demonstrated the relevance of the POCIS for sampling hormones, pharmaceuticals and pesticides from a waste water treatment plant effluent. This thesis permits to improve knowledge on the POCIS and to promote its application for the water framework directive