EPR spectroscopy of iron- and nickel-doped [ZnAl]-layered double hydroxides: modeling active sites in heterogeneous water oxidation catalysts

Iron-doped nickel layered double hydroxides (LDHs) are among the most active heterogeneous water oxidation catalysts. Due to inter-spin interactions, however, the high density of magnetic centers results in line-broadening in magnetic resonance spectra. As a result, gaining atomic-level insight into the catalytic mechanism via electron paramagnetic resonance (EPR) is not generally possible. To circumvent spin-spin broadening, iron and nickel atoms were doped into non-magnetic [ZnAl]-LDH materials and the coordination environments of the isolated Fe(III) and Ni(II) sites were characterized. Multifrequency EPR spectroscopy identified two distinct Fe(III) sites (S = 5/2) in [Fe:ZnAl]-LDH. Changes in zero field splitting (ZFS) were induced by dehydration of the material, revealing that one of the Fe(III) sites is solvent-exposed (i.e. at an edge, corner, or defect site). These solvent-exposed sites feature an axial ZFS of 0.21 cm⁻¹ when hydrated. The ZFS increases dramatically upon dehydration (to -1.5 cm⁻¹), owing to lower symmetry and a decrease in the coordination number of iron. The ZFS of the other (“inert”) Fe(III) site maintains an axial ZFS of 0.19-0.20 cm⁻¹ under both hydrated and dehydrated conditions. We observed a similar effect in [Ni:ZnAl]-LDH materials; notably, Ni(II) (S = 1) atoms displayed a single, small ZFS (±0.30 cm⁻¹) in hydrated material, whereas two distinct Ni(II) ZFS values (±0.30 and ±1.1 cm⁻¹) were observed in the dehydrated samples. Although the magnetically-dilute materials were not active catalysts, the identification of model sites in which the coordination environments of iron and nickel were particularly labile (e.g. by simple vacuum drying) is an important step towards identifying sites in which the coordination number may drop spontaneously in water, a probable mechanism of water oxidation in functional materials

Stress, health, noise exposures, and injuries among electronic waste recycling workers in Ghana

Abstract Background Electronic waste (e-waste) recycling workers in low and middle-income countries have the potential for occupational injuries due to the nature of their work at informal e-waste sites. However, limited research exists on stress, noise, occupational injuries, and health risks associated with this work environment. This study evaluated injury experience, noise exposures, and stress risk factors among e-waste workers at the large recycling site in the Agbogbloshie market, Accra, Ghana. Methods Participants completed a survey addressing their work, health status, stress, exposures to several occupational hazards (including noise), use of personal protective equipment at work, and injury experience. A subset of participants also completed personal noise dosimetry measurements. Poisson regression was used to evaluate the association between the number of injuries experienced by participants and various factors evaluated in the survey. Results Forty-six male e-waste workers completed the survey, and 26 completed a noise dosimetry measurement. Participants experienced an average of 9.9 ± 9.6 injuries per person in the previous 6 months (range: 1–40). The majority of injuries were lacerations (65.2%), and the most common injury location was the hand (45.7%). Use of personal protective equipment was rare. The mean time-weighted average noise level was 78.8 ± 5.9 dBA. Higher perceived stress, greater age, poorer health status, not using gloves, and involvement in dismantling activities were associated with an increased number of injuries. After controlling for each of these risk factors, perceived stress level and perceived noise exposure were associated with a significantly greater number of injuries. Conclusions Our study identified a large number of injuries among informal e-waste recyclers, and we found that higher levels of perceived stress and perceived noise were associated with an increased number of occupational injuries, even after controlling for other injury risk factors.https://deepblue.lib.umich.edu/bitstream/2027.42/146778/1/12995_2018_Article_222.pd

EPR spectroscopy of iron- and nickel-doped [ZnAl]-layered double hydroxides: modeling active sites in heterogeneous water oxidation catalysts

Iron-doped nickel layered double hydroxides (LDHs) are among the most active heterogeneous water oxidation catalysts. Due to inter-spin interactions, however, the high density of magnetic centers results in line-broadening in magnetic resonance spectra. As a result, gaining atomic-level insight into the catalytic mechanism via electron paramagnetic resonance (EPR) is not generally possible. To circumvent spin-spin broadening, iron and nickel atoms were doped into non-magnetic [ZnAl]-LDH materials and the coordination environments of the isolated Fe(III) and Ni(II) sites were characterized. Multifrequency EPR spectroscopy identified two distinct Fe(III) sites (S = 5/2) in [Fe:ZnAl]-LDH. Changes in zero field splitting (ZFS) were induced by dehydration of the material, revealing that one of the Fe(III) sites is solvent-exposed (i.e. at an edge, corner, or defect site). These solvent-exposed sites feature an axial ZFS of 0.21 cm⁻¹ when hydrated. The ZFS increases dramatically upon dehydration (to -1.5 cm⁻¹), owing to lower symmetry and a decrease in the coordination number of iron. The ZFS of the other (“inert”) Fe(III) site maintains an axial ZFS of 0.19-0.20 cm⁻¹ under both hydrated and dehydrated conditions. We observed a similar effect in [Ni:ZnAl]-LDH materials; notably, Ni(II) (S = 1) atoms displayed a single, small ZFS (±0.30 cm⁻¹) in hydrated material, whereas two distinct Ni(II) ZFS values (±0.30 and ±1.1 cm⁻¹) were observed in the dehydrated samples. Although the magnetically-dilute materials were not active catalysts, the identification of model sites in which the coordination environments of iron and nickel were particularly labile (e.g. by simple vacuum drying) is an important step towards identifying sites in which the coordination number may drop spontaneously in water, a probable mechanism of water oxidation in functional materials

Injury Risk and Noise Exposure in Firefighter Training Operations

Introduction: Firefighters have high rate of injuries and illnesses, as well as exposures to high levels of noise. This study explored the relationship between noise exposure and injury among firefighters. Methods: We recruited firefighters undergoing vehicle extrication and structural collapse emergency response training at a highly realistic training facility. Demographics, health status, body mass index (BMI), and history of serious injuries (i.e. injuries requiring first aid treatment, treatment in a medical clinic or office, or treatment at a hospital) were assessed at baseline, and daily activities, injury events, and near misses were assessed daily via surveys. Participants’ noise exposures were monitored for one 24-h period using noise dosimeters. We used a mixed-effects logistic regression model to estimate the odds of injury events and near misses associated with noise exposure as an independent variable. Results: Of 56 subjects, 20 (36%) reported that they had ever suffered a serious injury during firefighting activities, and 9 (16%) reported a serious injury within the past year. We estimated rates of 6.6 lifetime serious injuries per 100 FTE 16.1 serious injuries per 100 FTE within the past year. Our models indicated a significant increase in injury events and near misses among those with higher BMI, and as well as a dose–response relationship between near misses/injuries and increasing noise levels. Noise levels >90 dBA in the 30 min prior to time of injury or near miss were associated with substantially increased odds ratios for injury or near miss. Our models further indicated that perceived job demands were significantly associated with increased risk of injury or near miss. Conclusion: Our results suggest that noise exposures may need to be incorporated into injury prevention programs for firefighters to reduce injuries among this high-risk occupational group.This research was supported by a pilot project research training grant from the Center for Occupational Health and Safety Engineering (COHSE) at the University of Michigan, an Education and Research Center supported by training grant No. 2T42OH008455 from the Centers for Disease Control and Prevention/National Institute for Occupational Safety and Health.Ope

Deep Underground Science and Engineering Laboratory - Preliminary Design Report

The DUSEL Project has produced the Preliminary Design of the Deep Underground Science and Engineering Laboratory (DUSEL) at the rehabilitated former Homestake mine in South Dakota. The Facility design calls for, on the surface, two new buildings - one a visitor and education center, the other an experiment assembly hall - and multiple repurposed existing buildings. To support underground research activities, the design includes two laboratory modules and additional spaces at a level 4,850 feet underground for physics, biology, engineering, and Earth science experiments. On the same level, the design includes a Department of Energy-shepherded Large Cavity supporting the Long Baseline Neutrino Experiment. At the 7,400-feet level, the design incorporates one laboratory module and additional spaces for physics and Earth science efforts. With input from some 25 science and engineering collaborations, the Project has designed critical experimental space and infrastructure needs, including space for a suite of multidisciplinary experiments in a laboratory whose projected life span is at least 30 years. From these experiments, a critical suite of experiments is outlined, whose construction will be funded along with the facility. The Facility design permits expansion and evolution, as may be driven by future science requirements, and enables participation by other agencies. The design leverages South Dakota's substantial investment in facility infrastructure, risk retirement, and operation of its Sanford Laboratory at Homestake. The Project is planning education and outreach programs, and has initiated efforts to establish regional partnerships with underserved populations - regional American Indian and rural populations

Oil and PCB interactions on the uptake and excretion in midges

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/47989/1/128_2005_Article_BF01625535.pd

A comparison of occupational and nonoccupational noise exposures in Sweden

This study was conducted to evaluate noise exposures and the contributions of occupational and nonoccupational activities among three groups of Swedish workers (office workers, day care workers, and military flight technicians), and to evaluate risk factors for elevated hearing threshold levels. Forty-five subjects were recruited across the three groups. Each subject completed a risk factor questionnaire along with Békésy audiometry at frequencies between 125 and 8000 Hz. Subjects also wore a noise dosimeter continuously for 1 week, and documented their occupational and nonoccupational activities using a time-activity log. Subjects in all groups completed >7400 h of dosimetry, and had weekly exposures between 76 and 81 dBA. Day care workers had the highest daily exposures, and flight technicians had the highest weekly exposures. Most daily and weekly exposures exceeded the 70 dBA exposure limit recommended for prevention of any hearing loss. Subjects′ perceptions of their exposures generally agreed well with measured noise levels. Among office workers, exposures were predominately nonoccupational, while among flight technicians nonoccupational and occupational activities contributed roughly equally, and among day care workers occupational exposures were dominant. Extreme exposures and cumulative noise exposure were associated with an increased risk of hearing threshold levels >10 dB hearing level. Effective hearing loss prevention programs may be needed in occupations not historically considered to be at high risk of noise-induced hearing loss (e.g., day care workers). Prevention efforts need to address nonoccupational exposures as well as occupational exposures, as nonoccupational activities may present the dominant risk of noise-induced hearing loss for some workers

Characterization of a unique polysaccharide monooxygenase from the plant pathogen Magnaporthe oryzae.

Blast disease in cereal plants is caused by the fungus Magnaporthe oryzae and accounts for a significant loss in food crops. At the outset of infection, expression of a putative polysaccharide monooxygenase (MoPMO9A) is increased. MoPMO9A contains a catalytic domain predicted to act on cellulose and a carbohydrate-binding domain that binds chitin. A sequence similarity network of the MoPMO9A family AA9 showed that 220 of the 223 sequences in the MoPMO9A-containing cluster of sequences have a conserved unannotated region with no assigned function. Expression and purification of the full length and two MoPMO9A truncations, one containing the catalytic domain and the domain of unknown function (DUF) and one with only the catalytic domain, were carried out. In contrast to other AA9 polysaccharide monooxygenases (PMOs), MoPMO9A is not active on cellulose but showed activity on cereal-derived mixed (1→3, 1→4)-β-D-glucans (MBG). Moreover, the DUF is required for activity. MoPMO9A exhibits activity consistent with C4 oxidation of the polysaccharide and can utilize either oxygen or hydrogen peroxide as a cosubstrate. It contains a predicted 3-dimensional fold characteristic of other PMOs. The DUF is predicted to form a coiled-coil with six absolutely conserved cysteines acting as a zipper between the two α-helices. MoPMO9A substrate specificity and domain architecture are different from previously characterized AA9 PMOs. The results, including a gene ontology analysis, support a role for MoPMO9A in MBG degradation during plant infection. Consistent with this analysis, deletion of MoPMO9A results in reduced pathogenicity

Trapping and Electron Paramagnetic Resonance Characterization of the 5dAdo• Radical in a Radical S-Adenosyl Methionine Enzyme Reaction with a Non-Native Substrate.

S-Adenosyl methionine (SAM) is employed as a [4Fe-4S]-bound cofactor in the superfamily of radical SAM (rSAM) enzymes, in which one-electron reduction of the [4Fe-4S]-SAM moiety leads to homolytic cleavage of the S-adenosyl methionine to generate the 5-deoxyadenosyl radical (5dAdo•), a potent H-atom abstractor. HydG, a member of this rSAM family, uses the 5dAdo• radical to lyse its substrate, tyrosine, producing CO and CN that bind to a unique Fe site of a second HydG Fe-S cluster, ultimately producing a mononuclear organometallic Fe-l-cysteine-(CO)2CN complex as an intermediate in the bioassembly of the catalytic H-cluster of [Fe-Fe] hydrogenase. Here we report the use of non-native tyrosine substrate analogues to further probe the initial radical chemistry of HydG. One such non-native substrate is 4-hydroxy phenyl propanoic acid (HPPA) which lacks the amino group of tyrosine, replacing the CαH-NH2 with a CH2 at the C2 position. Electron paramagnetic resonance (EPR) studies show the generation of a strong and relatively stable radical in the HydG reaction with natural abundance and 13C2-HPPA, with appreciable spin density localized at C2. These results led us to try parallel experiments with the more oxidized non-native substrate coumaric acid, which has a C2=C3 alkene substitution relative to HPPAs single bond. Interestingly, the HydG reaction with the cis-p-coumaric acid isomer led to the trapping of a new radical EPR signal, and EPR studies using cis-p-coumaric acid along with isotopically labeled SAM reveal that we have for the first time trapped and characterized the 5dAdo• radical in an actual rSAM enzyme reaction, here by using this specific non-native substrate cis-p-coumaric acid. Density functional theory energetics calculations show that the cis-p-coumaric acid has approximately the same C-H bond dissociation free energy as 5dAdo•, providing a possible explanation for our ability to trap an appreciable fraction of 5dAdo• in this specific rSAM reaction. The radicals EPR line shape and its changes with SAM isotopic substitution are nearly identical to those of a 5dAdo• radical recently generated by cryophotolysis of a prereduced [4Fe-4S]-SAM center in another rSAM enzyme, pyruvate formate-lyase activating enzyme, further supporting our assignment that we have indeed trapped and characterized the 5dAdo• radical in a radical SAM enzymatic reaction by appropriate tuning of the relative radical free energies via the judicious selection of a non-native substrate