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Background: In April 1991, an excess of bladder cancer cases among workers employed at a chemical manufacturing facility in Niagara Falls, NY, was reported. This excess was primarily confined to 708 workers who had ever been employed in the rubber chemicals manufacturing area of the plant, where the aromatic amines aniline and o-toluidine have historically been used. Purpose: An environmental and biological monitoring survey was conducted to evaluate current exposures to aniline and o-toluidine in the rubber chemicals department. Methods: Personal air sampling for aniline and o-toluidine was conducted with the use of a modified Occupational Safety and Health Administration (OSHA) 73 method. Urine samples were collected before and after work (i.e., pre-shift and post-shift, respectively) and stored at -70 [degrees]C. Base hydrolysis was used to convert acetanilide and N-acetyl-o-toluidine, metabolises of aniline and o-toluidine present in the urine, to the parent compounds. The parent compounds were extracted from the alkaline urine into butyl chloride and then back-extracted from the butyl chloride into aqueous hydrochloric acid. An aliquot of each acidic extract was subjected to ion-interaction reversed-phase liquid chromatography with coulometric electrochemical detection. Hemoglobin (Hb) was extracted from blood and stored at -70 [degrees]C. For the measurement of adducts of aniline, o-toluidine, and 4-aminobiphenyl (4-ABP), precipitated Hb was dissolved in 0.1 M sodium hydroxide in the presence of recovery standards, and the hydrolysate was extracted with hexane, derivatized with pentafluoropropionic anhydride, and analyzed by gas chromatography-mass spectrometry with negative chemical ionization. Results: A total of 73 workers, including 46 of 64 exposed workers who were employed in the rubber chemicals department and had the potential for exposure to aniline and o-toluidine and 27 of 52 unexposed workers employed in other departments where aniline and otoluidine were not used or produced, had data available for both aniline and o-toluidine and Hb adducts; 28 of the workers in the former group also had personal air-sampling data. Personal air sample measurements showed that airborne concentrations of aniline and o-toluidine were well within the limits allowed in the workplace by OSHA. Urinary aniline and o-toluidine levels, however, were substantially higher among exposed workers than among unexposed control subjects. The most striking differential was for post-shift urinary o-toluidine levels, which averaged (+ standard deviation) 2.8 [mu]g/L (+-1.4 [mu]g/L) in unexposed subjects and 98.7 [mu]g/L (+-119.4 [mu]g/L) in exposed subjects (P = .0001). Average aniline-Hb and o-toluidine-Hb adduct levels were also significantly higher (P = .0001) among exposed workers than among unexposed control subjects. Average levels of adducts to 4-ABP, a potential contaminant of process chemicals, were not significantly different (P = .48), although three exposed workers had 4-ABP levels above the range in unexposed workers. Conclusions: The adduct data suggest that, among current workers, o-toluidine exposure substantially exceeds aniline exposure and that 4-ABP exposure, if it occurs at all, is not widespread. These data support the conclusion that occupational exposure to o-toluidine is the most likely causal agent of the bladder cancer excess observed among workers in the rubber chemicals department of the plant under study, although exposures to aniline and 4-ABP cannot be ruled out.

The use of ceramics bearings in total hip joint replacement (THR) has increased markedly in the last ten years thanks to the optimum wear behaviour of ceramic-on-ceramic bearings and of the high biological safety of ceramic wear debris. As the number of ceramic THR bearings is increasing, also the number of implants that experience off-normal working conditions, e.g. edge loading, third bodies in the joint, soft tissues laxity, dislocation/subluxation of the joint, increases. Under all such conditions the surface of the bearing can be damaged to variable extent, leading eventually to a limitation of the expected performances of the implant.

We studied the role of cytokines (TNF-α, IL-6,IL-1β, TGF-β) as markers of osteolysis in patients who underwent to a hip prosthesis implantation subdivided in two groups: group A with an ultrahigh molecular weight polyethylene (UHMWPE) insert articulating against a metal ball head , and group B with an all alumina ceramic combination. Profibrogenic (TGF-β) and pro-inflammatory cytokines (TNF-α, IL-6,IL-1β) are secreted by the periprosthetic synovial-like fibrous membrane in hip artificial implants. They are secreted by inflammatory activated cells and trigger the cascade of biochemical events leading to the activation of osteoclasts and bone resorption. A statistically significant increase of TGF-β serum levels was observed between TGF-β values in implanted patients as compared to normal subjects and between TGF-β values after versus before implantation in Group A. A progressive decrease in TNF-α and IL-6 serum levels has been observed in both Groups, when compared with the initial values before the implantation. IL-1β levels decreased up to 60 months after the implantation Our data suggest that monitoring circulating cytokines could be a good indicator for the proliferation and activity of the periprosthetic synovial-like membrane and potential osteolysis. This could allow for an adequate early treatment.

Isocyanates may cause contact dermatitis, sensitization and asthma. Dermal exposure to aliphatic and aromatic isocyanates can occur in various exposure settings. The fate of isocyanates on skin is an important unanswered question. Do they react and bind to the outer layer of skin or do they penetrate through the epidermis as unreacted compounds? Knowing the kinetics of these processes is important in developing dermal exposure sampling or decontamination strategies, as well as understanding potential health implications such exposure may have. In this paper the residence time of model isocyanates on hairless guinea pig skin was investigated in vitrousing attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry. Model isocyanates tested were octyl isocyanate, polymeric hexamethylene diisocyanate isocyanurate (pHDI), polymeric isophorone diisocyanate isocyanurate (pIPDI) and methylenediphenyl diisocyanate (MDI). Isocyanates in ethyl acetate (30 μL) were spiked directly on the skin to give 0.2–1.8 μmol NCO cm−2(NCO = –NCO), and absorbance of the isocyanate group and other chemical groups of the molecule were monitored over time. The ATR-FTIR findings showed that polymeric isocyanates pHDI and pIPDI may remain on the skin as unreacted species for many hours, with only 15–20% of the total isocyanate group disappearing in one hour, while smaller compounds octyl isocyanate and MDI rapidly disappear from the skin surface (80+% in 30 min). Isocyanates most likely leave the skin surface by diffusion predominantly, with minimal reaction with surface proteins. The significance of these findings and their implications for dermal exposure sampling and isocyanate skin decontamination are discussed.

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