Chromium released from leather - II: the importance of environmental parameters.
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ABSTRACT: Background
Approximately 1-3% of the adult population in Europe are allergic to chromium (Cr). A new restriction in Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) based on the ISO 17075 standard has recently been adopted in the EU to limit Cr(VI) in consumer and occupational leather products to < 3 mg/kg.Objectives
To investigate the influence of storage conditions [relative humidity, temperature, ultraviolet (UV) irradiation, and duration] on Cr release, and to assess several parameters relevant for occupational exposure (repeated exposure, wear, alkaline solutions, and sequential wet and dry exposures).Material and methods
A leather of relevance for work gloves was investigated for its release of Cr(III) and Cr(VI) under these different experimental conditions.Results
Relative humidity (water content in leather) during storage prior to Cr extraction was the single most important parameter. Cr(VI) levels could vary from non-detectable to levels significantly exceeding the restriction limit, depending on the relative humidity. Leather contact with alkaline solution and UV irradiation during storage could increase the Cr(VI) levels in subsequent extractions.Conclusions
The amount of Cr(VI) in leather is not an intrinsic property, but is influenced by environmental conditions of relevance for occupations and skin exposure.
SUBMITTER: Mathiason F
PROVIDER: S-EPMC4964937 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:BackgroundApproximately 1-3% of the adult population in Europe is allergic to chromium (Cr). A new restriction in REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) based on the ISO 17075 standard has recently been adopted in the EU to limit Cr(VI) in consumer and occupational leather products.ObjectivesThe aim of this study was to critically assess key experimental parameters in this standard on the release of Cr(III) and Cr(VI) and their relevance for skin exposure.Material and methodsFour differently tanned, unfinished, leather samples were systematically investigated for their release of Cr(III) and Cr(VI) in relation to surface area, key exposure parameters, temperature, ultraviolet irradiation, and time.ResultsAlthough the total release of Cr was largely unaffected by all investigated parameters, except exposure duration and temperature, the Cr oxidation state was highly dynamic, with reduced amounts of released Cr(VI) with time, owing to the simultaneous release of reducing agents from the leather. Significantly more Cr(III) than Cr(VI) was released from the Cr-tanned leather for all conditions tested, and it continued to be released in artificial sweat up to at least 1 week of exposure.ConclusionsSeveral parameters were identified that influenced the outcome of the ISO 17075 test.
| S-EPMC4415597 | biostudies-literature
Project description:BackgroundChromium (Cr) release from Cr-tanned leather articles is a major cause of Cr contact dermatitis. It has been suggested that Cr(VI) release from leather is not necessarily an intrinsic property of the leather, but is strongly dependent on environmental conditions.ObjectivesTo test this hypothesis for long-term (8?months) simulated use.Materials and methodsThe release of total Cr and Cr(VI) from Cr-tanned, unfinished leather was analysed in subsequent phosphate buffer (pH?8.0) immersions for a period of 7.5?months. The effect of combined ultraviolet treatment and alkaline solution (pH?12.1) was tested. Dry storage [20% relative humidity (RH)] was maintained between immersions. Atomic absorption spectroscopy, X-ray fluorescence and diphenylcarbazide tests were used.ResultsCr(VI) release was dependent on previous dry storage or alkaline treatment, but not on duration or number of previous immersions. Cr(III) release decreased with time. Fifty-two percent of the total Cr released during the last immersion period was Cr(VI). Cr(VI) release exceeded 9?mg/kg in all immersion periods except in the first 10-day immersion (2.6?mg/kg).ConclusionsCr(VI) release is primarily determined by environmental factors (RH prior to immersion, solution pH, and antioxidant content). The RH should be kept low prior to testing Cr(VI) release from leather.
| S-EPMC5084788 | biostudies-literature
Project description:BACKGROUND:Chromium (Cr) is a common skin sensitizer. The use of Cr(VI) in leather is restricted in the EU, but that of Cr(III) is not. OBJECTIVES:To assess whether prolonged exposure to Cr-tanned leather with mainly Cr(III) release may elicit allergic contact dermatitis in Cr-allergic individuals. METHOD:Ten Cr-allergic subjects and 22 controls were patch tested with serial dilutions of Cr(III) and Cr(VI), and with leather samples. They then conducted a use test with a Cr-tanned and a Cr-free leather bracelet over a period of 3?weeks, for 12?h per day. Cr deposited on the skin from the bracelets was measured in the controls, and the diphenylcarbazide test for Cr(VI) and extraction tests for Cr(III) and Cr(VI) were conducted for the different leathers. RESULTS:Four of 10 Cr-allergic subjects developed positive reactions to the Cr-tanned bracelet within 7-21?days, whereas only 1 of 10 had a positive patch test reaction to this leather. Cr released from the Cr-tanned leather was most probably entirely Cr(III), with a quantifiable amount being deposited on the skin. CONCLUSIONS:This study strongly suggests that prolonged and repeated exposure to Cr-tanned leather with mainly Cr(III) release is capable of eliciting allergic contact dermatitis in Cr-allergic individuals.
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Project description:Laboratory experiments suggest that polymeric Cr(III) could exist in aqueous solution for a relative long period of time. However, the occurrence of polymeric Cr(III) has not been reported in environmental media due partially to the lack of method for speciating polymeric Cr. We observed an unknown Cr species during the course of study on speciation of Cr in the leachates of chromated-copper-arsenate (CCA)-treated wood. Efforts were made to identify structure of the unknown Cr species. Considering the forms of Cr existed in the CCA-treated woods, we mainly focused our efforts to determine if the unknown species were polymeric Cr(III), complex of Cr/As or complex of Cr with dissolved organic matter (DOM). In order to evaluate whether polymeric Cr(III) largely exist in wood leachates, high performance liquid chromatography coupled with inductively coupled mass spectrometry (HPLC-ICPMS was used) for simultaneous speciation of monomeric Cr(III), polymeric Cr(III), and Cr(VI). In addition to wood leachates where polymeric Cr (III) ranged from 39.1 to 67.4%, occurrence of the unknown Cr species in other environmental matrices, including surface waters, tap and waste waters, was also investigated. It was found that polymeric Cr(III) could exist in environmental samples containing μg/L level of Cr, at a level up to 60% of total Cr, suggesting that polymeric Cr(III) could significantly exist in natural environments. Failure in quantifying polymeric Cr(III) would lead to the underestimation of total Cr and bias in Cr speciation. The environmental implication of the presence of polymeric Cr(III) species in the environment deserves further study.
| S-EPMC5027193 | biostudies-literature
Project description:With the intensification of fish farming, the amount of residues also increased. One of the by-products generated is leather. However, several factors influence its quality, among them, the types of tanning used. Paiche (Arapaima gigas) is the largest freshwater fish in the world, and therefore has great potential in the use of leather, in addition to being one of the most cultivated fish in the Rondônia state. The aimed was to evaluate the physicomechanical resistance, histological and morphological aspects in different directions of the fibers of the paiche to evaluate the tanning with chromium oxide and vegetable tannin. Paiches with an average weight of 12.0 kg were used, skins were made and tanned using chromium and vegetable tannin as techniques. After tanning, 20 specimens were removed in longitudinal, transverse and diagonal directions to the fish body, to determine resistance in dynamometer and leather for histological analysis, scanning electron microscopy and physical-chemical analysis. The average thickness of the specimens of the leathers ranged 1.79mm to 2.82mm, in addition, there was no interaction between the type of tanning agent and the directions obtained for strength, traction and elongation. Regarding the progressive tearing test, there was also no interaction effect. However, the defined factors had relevant differences for the maximum and average amount applied, and the leathers tanned with vegetable tannin expanded to larger dimensions 110.19 and 85.52 N. According to the images obtained by histology and scanning microscopy, they presented that in the longitudinal and transverse direction the collagen fibers are presented in layers parallel to the leather surface and in the diagonal direction the interlacing is more intense, that is, in addition to the overlapping layers intercalated thinner, close to the surface, fiber bundles can also be seen crossing each other. It is concluded that leathers tanned with vegetable tannin have less resistance than leathers tanned with chromium salts for traction to rupture and greater resistance to tear.
| S-EPMC8782319 | biostudies-literature
Project description:Collagen-based polymers and their blends have attracted considerable interest for new materials development due to their unique combination of biocompatibility, physical and mechanical properties and durability. Leather, a modified natural biopolymer made from animal rawhide and the first synthetic collagen-based polymer known since the dawn of civilization, combines all these features. Rawhide is transformed into leather by tanning, a process in which the collagen is cross-linked with different agents to make it stronger and more durable and to prevent its decay. Research on the development of environmentally friendly procedures and sustainable materials with higher efficiency and lower costs is a rapidly growing field, and leather industry is not an exemption. Chrome-tanned and vegetable-tanned (chromium-free) shavings from the leather industry present a high content of organic matter, yet they are considered recalcitrant waste to be degraded by microbiological processes like anaerobic digestion (AD), a solid technology to treat organic waste in a circular economy framework. In this technology however, the solubilisation of organic solid substrates is a significant challenge to improving the efficiency of the process. In this context, we have investigated the process of microbial decomposition of leather wastes from the tannery industry to search for the conditions that produce optimal solubilisation of organic matter. Chrome-tanned and chromium-free leather shavings were pre-treated and anaerobically digested under different temperature ranges (thermophilic-55 °C-, intermediate-42 °C- and mesophilic-35 °C) to evaluate the effect on the solubilisation of the organic matter of the wastes. The results showed that the presence of chromium significantly inhibited the solubilization (up to 60%) in the mesophilic and intermediate ranges; this is the fastest and most efficient solubilization reached under thermophilic conditions using the chromium-free leather shaving as substrates. The most suitable temperature for the solubilization was the thermophilic regime (55 °C) for both chromium-free and chrome-tanned shavings. No significant differences were observed in the thermophilic anaerobic digestion of chromium-free shavings when a pre-treatment was applied, since the solubilisation was already high without pre-treatment. However, the pre-treatments significantly improved the solubilisation in the mesophilic and intermediate configurations; the former pre-treatment was better suited in terms of performance and cost-effectiveness compared to the thermophilic range. Thus, the solubilisation of chromium-free tannery solid wastes can be significantly improved by applying appropriate pre-treatments at lower temperature ranges; this is of utter importance when optimizing anaerobic processes of recalcitrant organic wastes, with the added benefit of substantial energy savings in the scaling up of the process in an optimised circular economy scenario.
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Project description:Environmental sanitation in food manufacturing plants promotes food safety and product microbial quality. However, the development of experimental models remains a challenge due to the complex nature of commercial cleaning processes, which include spraying water and sanitizer on equipment and structural surfaces within manufacturing space. Although simple in execution, the physical driving forces are difficult to simulate in a controlled laboratory environment. Here, we present a bench-scale bioreactor system which mimics the flow conditions in environmental sanitation programs. We applied computational fluid dynamic (CFD) simulations to obtain fluid flow parameters that better approximate and predict industrial outcomes. According to the CFD model, the local wall shear stress achieved on the target surface ranged from 0.015 to 5.00 Pa. Sanitation efficacy on six types of environmental surface materials (hydrophobicity, 57.59 to 88.61°; roughness, 2.2 to 11.9 μm) against two different microbial targets, the bacterial pathogen Listeria monocytogenes and Exophiala species spoilage fungi, were evaluated using the bench-scale bioreactor system. The relative reduction ranged from 0.0 to 0.82 for Exophiala spp., which corresponded to a 0.0 to 2.21 log CFU/coupon reduction, and the relative reduction ranged from 0.0 to 0.93 in L. monocytogenes which corresponded to a 0.0 to 6.19 log CFU/coupon reduction. Although most treatment parameters were considered statistically significant against either L. monocytogenes or Exophiala spp., contact time was ranked as the most important predictor for L. monocytogenes reduction. Shear stress contributed the most to Exophiala spp. removal on stainless steel and Buna-N rubber, while contact time was the most important factor on HDPE (high-density polyethylene), cement, and epoxy.IMPORTANCE Commercial food manufacturers commonly employ a single sanitation program that addresses both bacterial pathogen and fungal spoilage microbiota, despite the fact that the two microbial targets respond differently to various environmental sanitation conditions. Comparison of outcome-based clusters of treatment combinations may facilitate the development of compensatory sanitation regimes where longer contact time or greater force are applied so that lower sanitizer concentrations can be used. Determination of microbiological outcomes related to sanitation program efficacy against a panel of treatment conditions allows food processors to balance tradeoffs between quality and safety with cost and waste stream management, as appropriate for their facility.
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Project description:Single crystals of the title compound, Pb(2)CrF(7), were obtained by solid-state reaction. The monoclinic structure is isotypic with Pb(2)RhF(7) and is built up of CrF(6) (3-) octa-hedra isolated from each other, inserted in a fluorite-related matrix of PbF(6) distorted octa-hedra, and PbF(8) square anti-prisms sharing edges and corners. The seventh F atom is 'independent', connected only to three Pb atoms within FPb(3) triangles, sharing an edge and building an almost planar Pb(4)F(2) unit, so that the formula can alternatively be written as Pb(2)F(CrF(6)).
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Project description:Leather waste (BF) and high-density polyethylene (HDPE) were compounded in a lab scale internal mixer and processed by means of injection molding. In this study, leather waste and HDPE composites were characterized by instrumental techniques such as differential scanning calorimetry (DSC), thermo-gravimetric Analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). Physical integrity of composites against chemical exposure and chromium-leaching properties of the composites were also investigated. This study shows that the incorporation of 30% leather waste fiber into HDPE composites decreases the thermal conductivity of the composite samples by 17% in comparison to that of neat HDPE samples. Composites showed no thermal degradation during processing cycle. Strong interfacial bonding between leather waste and polymer results in comparable low-leachate levels to maximum allowed concentration for nonhazardous waste, and good chemical resistance properties. The BF/HDPE composites could be a promising low-cost alternative in industrial application areas of HDPE, where high-mechanical strength and low-thermal conductivity is required.
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Project description:The combination of π-donating amido with π-accepting pyridine coordination units in a tridentate chelate ligand causes a strong nephelauxetic effect in a homoleptic CrIII complex, which shifts its luminescence to the NIR-II spectral range. Previously explored CrIII polypyridine complexes typically emit between 727 and 778 nm (in the red to NIR-I spectral region), and ligand design strategies have so far concentrated on optimizing the ligand field strength. The present work takes a fundamentally different approach and focusses on increasing metal-ligand bond covalence to shift the ruby-like 2 E emission of CrIII to 1067 nm at 77 K.
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