XRF measurements of tin, copper and zinc in antifouling paints coated on leisure boats.

Tributyltin (TBT) and other organotin compounds have been restricted for use on leisure boats since 1989 in the EU. Nonetheless, release of TBT is observed from leisure boats during hull maintenance work, such as pressure hosing. In this work, we used a handheld X-ray Fluorescence analyser (XRF) calibrated for antifouling paint matrixes to measure tin, copper and zinc in antifouling paints coated on leisure boats in Sweden. Our results show that over 10% of the leisure boats (n = 686) contain >400 µg/cm(2) of tin in their antifouling coatings. For comparison, one layer (40 µm dry film) of a TBT-paint equals ≈ 800 µg Sn/cm(2). To our knowledge, tin has never been used in other forms than organotin (OT) in antifouling paints. Thus, even though the XRF analysis does not provide any information on the speciation of tin, the high concentrations indicate that these leisure boats still have OT coatings present on their hull. On several leisure boats we performed additional XRF measurements by progressively scraping off the top coatings and analysing each underlying layer. The XRF data show that when tin is detected, it is most likely present in coatings close to the hull with several layers of other coatings on top. Thus, leaching of OT compounds from the hull into the water is presumed to be negligible. The risk for environmental impacts arises during maintenance work such as scraping, blasting and high pressure hosing activities. The data also show that many boat owners apply excessive paint layers when following paint manufacturers recommendations. Moreover, high loads of copper were detected even on boats sailing in freshwater, despite the more than 20 year old ban, which poses an environmental risk that has not been addressed until now.

Jewellery: alloy composition and release of nickel, cobalt and lead assessed with the EU synthetic sweat method.

BACKGROUND: Several studies have shown nickel and cobalt release from jewellery by using spot tests, but the metal composition of jewellery is largely unknown. OBJECTIVES: To evaluate the metal composition of a large worldwide sample of mainly inexpensive jewellery items, and investigate the release of nickel, cobalt and lead from a subsample by using EN 1811:1998-required methods. METHODS: A total of 956 metallic jewellery components were examined with X-ray fluorescence spectroscopy. A subsample of 96 jewellery items purchased in the United States were investigated for nickel, cobalt and lead release by the use of artificial sweat immersion and plasma optical emission spectroscopy. RESULTS: Eighteen elements were detected. The 10 most frequently occurring were, in order of frequency, copper, iron, zinc, nickel, silver, chromium, tin, manganese, lead, and cobalt. Release of nickel was noted from 79 of the 96 US samples (0.01-98 µg/cm(2) /week), release of cobalt from 35 samples (0.02-0.5 µg/cm(2) /week), and release of lead from 37 samples (0.03-2718 µg/cm(2) /week). CONCLUSIONS: We present here a comprehensive list of the most frequently encountered metals in jewellery and fashion accessories. Different allergenic and non-allergenic metals are utilized. We also report the frequent release of nickel, cobalt and lead from these objects, despite legislative restrictions.

New analytical application for metal determination in antifouling paints.

Despite the ban of applying TBT coatings on leisure boats in the late 80s, recent studies show an ongoing spread of TBT from leisure boats, particularly during hull cleaning events. Therefore, countries in EU have adopted expensive measures to clean this wash water. A more cost-efficient measure is to focus directly on the source, i.e. identify leisure boats with high concentrations of TBT and prescribe boat owners to remove the paint. We have developed a new antifouling paint application for a handheld X-ray fluorescence (XRF) analyzer to be used for identifying boats with high area concentrations (µg/cm(2)) of Sn (indication that the hull contains TBT paint residues). Copper and zinc are also included in the application since these metals are used in the vast majority of today's paints. A blind test with up to four layers of TBT-, copper- and zinc-based paints showed good correlation between XRF-measured area concentrations and chemically analyzed concentrations. Future usage of the applications involves identification of boat hulls in particular with high Sn concentrations and also with high Cu and Zn concentrations. This method has the potential to become a useful tool in regulatory management of existence and use of toxic elements on boat hulls.

Formal recycling of e-waste leads to increased exposure to toxic metals: an occupational exposure study from Sweden.

Electrical and electronic waste (e-waste) contains multiple toxic metals. However, there is currently a lack of exposure data for metals on workers in formal recycling plants. The objective of this study was to evaluate workers' exposure to metals, using biomarkers of exposure in combination with monitoring of personal air exposure. We assessed exposure to 20 potentially toxic metals among 55 recycling workers and 10 office workers at three formal e-waste recycling plants in Sweden. Workers at two of the plants were followed-up after 6 months. We collected the inhalable fraction and OFC (37-mm) fraction of particles, using personal samplers, as well as spot samples of blood and urine. We measured metal concentrations in whole blood, plasma, urine, and air filters using inductively coupled plasma-mass spectrometry following acid digestion. The air sampling indicated greater airborne exposure, 10 to 30 times higher, to most metals among the recycling workers handling e-waste than among the office workers. The exposure biomarkers showed significantly higher concentrations of chromium, cobalt, indium, lead, and mercury in blood, urine, and/or plasma of the recycling workers, compared with the office workers. Concentrations of antimony, indium, lead, mercury, and vanadium showed close to linear associations between the inhalable particle fraction and blood, plasma, or urine. In conclusion, our study of formal e-waste recycling shows that workers performing recycling tasks are exposed to multiple toxic metals.

Failure of total hip implants: metals and metal release in 52 cases.

BACKGROUND: The pathogenesis of total joint replacement failure is multifactorial. One hypothesis suggests that corrosion and wear of alloys result in metal ion release, which may then cause sensitization and even implant failure, owing to the acquired immune reactivity. OBJECTIVES: To assess cobalt, nickel and chromium(VI) release from, and the metal composition of, failed metal-on-ethylene total hip replacements. MATERIALS/METHODS: Implant components from 52 revision cases were evaluated with spot tests for free nickel, cobalt, and chromium (VI) ions. Implant composition was determined with X-ray fluorescence spectroscopy, and information on the reason for revision and complications in relation to surgery was collected from the medical charts when possible (72%). For 10 implants, corrosion was further characterized with scanning electron microscopy. RESULTS: We detected cobalt release from three of 38 removed femoral heads and from one of 24 femoral stems. Nickel release was detected from one of 24 femoral stems. No chromium(VI) release was detected. CONCLUSIONS: We found that cobalt and nickel were released from some failed total hip arthroplasties, and corrosion was frequently observed. Metal ions and particles corroded from metal-on-polyethylene may play a role in the complex aetiopathology of implant failure.

Do insulation products of man-made vitreous fibres still cause skin discomfort?

BACKGROUND: Man-made vitreous fibres (MMVFs) are used in products for insulation and as reinforcement in materials. Contamination of the skin may arise through direct or indirect contact, and from the deposition of airborne fibres. The scientific basis regarding the effects on skin of MMVFs dates from 1970-1980. OBJECTIVES: To investigate whether currently used insulation MMVF products still cause skin discomfort. METHODS: Focus group interviews and structured interviews were performed among workers engaged in insulation tasks and among do-it-yourself consumers with a recent experience of MMVF products. RESULTS: A majority of interviewees experienced skin discomfort when handling MMVF products. Complaints caused by traditional (yellow) glass fibre products were more severe than those caused by products of rock or slag wool fibres. The wrists, forearms, neck and face were the locations where the skin was most affected. The situations causing problems varied between occupational tasks, but working with the hands over the head or in narrow spaces were described as the worst situations. Building construction apprentices performed insulation tasks more often than senior workers. CONCLUSIONS: MMVF insulation products do still cause skin discomfort. Updated knowledge about people's experiences of work with such products should influence legislation.

Sensitivity and specificity of the nickel spot (dimethylglyoxime) test.

BACKGROUND: The accuracy of the dimethylglyoxime (DMG) nickel spot test has been questioned because of false negative and positive test reactions. The EN 1811, a European standard reference method developed by the European Committee for Standardization (CEN), is fine-tuned to estimate nickel release around the limit value of the EU Nickel Directive from products intended to come into direct and prolonged skin contact. Because assessments according to EN 1811 are expensive to perform, time consuming, and may destruct the test item, it should be of great value to know the accuracy of the DMG screening test. OBJECTIVES: To evaluate the sensitivity and specificity of the DMG test. METHODS: DMG spot testing, chemical analysis according to the EN 1811 reference method, and X-ray fluorescence spectroscopy (XRF) were performed concomitantly on 96 metallic components from earrings recently purchased in San Francisco. RESULTS: The sensitivity of the DMG test was 59.3% and the specificity was 97.5% based on DMG-test results and nickel release concentrations determined by the EN 1811 reference method. CONCLUSIONS: The DMG test has a high specificity but a modest sensitivity. It may serve well for screening purposes. Past exposure studies may have underestimated nickel release from consumer items.

Large organic aerosols in a dynamic and continuous whole-body exposure chamber tested on humans and on a heated mannequin.

Exposure to large airborne organic aerosols may cause respiratory and skin symptoms. The use of human exposure chambers permits safe mechanistic studies of the effect of inhalation or dermal deposition of such particles. The performance of a dynamic and continuous whole-body human exposure chamber using turbulent air mixing during exposure to these organic aerosols of humans and of a new heated mannequin was evaluated. Variability of temporal and spatial distribution of the airborne particle concentration, and aerodynamic aerosol size distribution of the inhalable fraction, were evaluated. The temporal and spatial distribution of these aerosols close to the breathing zone during an exposure session was typically < or = 10%, which is low for airborne particles of this size. In a larger section around a human, only slightly higher spatial variation was found. Variability between exposure sessions was also low (< 10%). Only limited effect of relative humidity for the organic aerosols was observed. The aerodynamic particle size distribution curves differed slightly, but some were comparable to those in occupational environments. The outcome of the performance tests as measured with the heated mannequin was almost the same as with humans, indicating that the mannequin could be used in preparatory tests in this type of chamber.

Measuring dust on skin with a small vacuuming sampler--a comparison with other sampling techniques.

Airborne skin exposure to allergens and irritants may cause dermatitis. There are few methods for assessing skin exposure to airborne particles. We have modified and tested a vacuuming sampler for removing particles from the skin. The sampler was compared with two other skin and surface exposure sampling techniques. These were based on surrogate skin (a patch sampler-adhesive tape on an optical cover glass) and a tape stripping removal procedure. All three samplers measure the mass of dust on skin. Dust containing starch was deposited onto the skin in a whole-body exposure chamber. Samples were taken from forearms and shoulders and analysed using optical microscopy. With the different sampling techniques small differences in the results were obtained. Agreement between the vacuuming sampler and the tape stripping technique was good. The comparison between patch and tape stripping procedure indicated a slight overestimation for the patch. The three techniques are applicable for assessing skin exposure to particles and for dose-effect studies. The vacuuming method will be further developed and applied in workplace studies. The technique allows for dust sampling from large areas of skin.

Wheat flour exposure results in recruitment of inflammatory cells in the lungs of healthy individuals.

BACKGROUND: Flour dust in bakeries is known to cause allergic as well as nonallergic respiratory symptoms. Fungal alpha-amylase is a commonly used baking additive that has been shown to have allergenic properties. The aim of this study was to investigate any effects on bronchoalveolar lavage (BAL) cells and peripheral blood lymphocytes (PBL) of healthy individuals exposed to airborne wheat flour dust with or without fungal alpha-amylase added. METHODS: Fifteen subjects were exposed during 1 hr in an exposure chamber, ten individuals to wheat flour alone and five with alpha-amylase added. BAL was performed 2-6 weeks before and 1 day after the exposure. BAL cells were differentially counted and flowcytometric analysis of the expression of activation, adhesion, and subset markers on alveolar macrophages (AM) and T cells in BAL fluid and peripheral blood were carried out. RESULTS: Exposure to wheat flour dust increased the total number of cells in BAL fluid from 75.4 (i.q. range 70.4-104.1) to 127.4 (92.1-187.4) cells x 10(6)/L, P < 0.01. There was a significant difference in the change of total BAL cell concentration between the study group exposed to wheat flour only (n = 10; increase with 91.9 x 10(6)/L) and the group exposed to wheat flour with the baking additive fungal alpha-amylase (n = 5; decrease with 5.4 x 10(6)/L). The exposure level of respirable dust was lower in the group that received alpha-amylase and the increase in BAL cell concentration showed a positive correlation with the concentration of respirable dust in the exposure chamber (r = 0.80, P < 0.001). The phenotypic analysis of AM indicated an influx of monocytic cells. CONCLUSIONS: The results indicate that the concentration of respirable dust, but not alpha-amylase, is of importance for the recruitment of inflammatory cells to the peripheral airways in healthy individuals exposed to wheat flour dust.