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The synthesis and employment of volatile toxic compounds as chemical weapons with a large-scale destructive power has introduced a new insidious threat over the last century. In this framework, the development of wearable sensing tools represents a critical point within the security field, in order to provide early alarm systems. Herein, a novel wearable electrochemical biosensor was developed for the rapid and on-site detection of mustard agents. Since a chemical attack is typically carried out by spraying these volatile agents into air, the sensor was designed in order to be able to measure mustard agents directly in the aerosol phase, further than in the liquid phase. The electrodes were screen-printed onto a filter paper support, which allowed to harness the porosity of paper to pre-load all the needed reagents into the cellulose network, and hence to realise an origami-like and reagent-free device. Mustard agent detection was carried out by monitoring their inhibitory effects toward the choline oxidase enzyme, through the amperometric measurement of the enzymatic by-product hydrogen peroxide. A carbon black/Prussian blue nanocomposite was used as a bulk-modifier of the conductive graphite ink constituting the working electrode, allowing for the electrocatalysis of the hydrogen peroxide reduction. After having verified the detecting capability toward a mustard agent simulant, the applicability of the resulting origami-like biosensor was demonstrated for the rapid and real-time detection of real sulfur mustard, obtaining limits of detection equal to 1 mM and 0.019 g·min/m3 for liquid and aerosol phase, respectively.

Exposure to trace metals in airborne particulate matter (PM) has been linked to various adverse health effects. Quantifying metals in PM is important; however, current analytical tools tend to be bulky and expensive. A need therefore exists for more rapid, low-cost, portable tools for multiplexed determination of metals in PM. Electrochemical paper-based devices (ePADs) have been used for detecting metals in PM but require different devices and methods for different metals, making the systems more complicated than desired. Recently reported Janus ePADs offer a solution to this problem by allowing for multiple electrochemical experiments from a single sample. Here, we sought to determine if a Janus ePAD containing four independent channels and working electrodes could be used for simultaneous detection of multiple metals in PM. Online sample pretreatment in each channel during sample delivery yielded optimal conditions for each experiment. The design allows the device to conduct square-wave anodic stripping voltammetry (SWASV) and square-wave cathodic stripping voltammetry (SWCSV) for simultaneous detection of Cd, Pb, Cu, Fe, and Ni from a single sample. Two detection zones each with shared reference and counter electrodes were used for SWASV and SWCSV, respectively. The proposed sensors reached LODs down to 0.5, 0.5, 1.0, 0.5, and 1.0 μg L

Immunoassays and high-performance liquid chromatography (HPLC) coupled with mass spectrometry (MS) are both widely used methods for drug screening in toxicology. We investigated an alternative approach for rapid drug screening: paper spray MS (PS-MS). In paper spray, the biofluid sample is spotted onto a paper substrate. Upon application of a spray solvent and an electric potential, extraction and ionization occur directly from the paper without any need for additional sample preparation. We developed two paper spray high-resolution MS/MS targeted drug screening assays using a quadrupole-orbitrap mass spectrometer, one the positive ion mode and one in the negative ion mode. In the positive ion mode, over 130 drugs and drug metabolites were semi-quantitatively screened at sub-toxic concentrations in a single 2.5 min analysis. Limits of detection and calibration performances for each target compound are reported. The PS-MS/MS assay was tested on authentic postmortem specimens, and its screening ability and semi-quantitative performance were evaluated against independent LC-MS-MS screening and confirmation assays with good agreement. The paper spray MS/MS showed good qualitative agreement with LC-MS-MS; the true positive rate of paper spray MS/MS was 92%, and the true negative rate was over 98%. The quantitative results between the two methods were also acceptable for a screening application; Passing-Bablok regression yielded a slope of 1.17 and a Pearson's correlation coefficient of 0.996. A separate PS-MS/MS negative ion screening method was also developed for a small panel of barbiturates and structural analogs, demonstrating its potential for acidic drug detection and screening.

Thermal papers (e.g. point of sale receipts, adhesive labels, tickets) significantly contribute to contamination of paper material cycles and the environment with substances of (eco-) toxicological concern. In particular, they contain color developers like endocrine disrupting bisphenols in typical concentrations of about 1–2 percent per weight (wt%). Bisphenol A (BPA) was used as the common color developer over the last decades, but it will be restricted for thermal paper application in the European Union to a limit of 0.02 wt% from 2020 onwards. Consequently, a variety of BPA substituents such as bisphenol S (BPS) and its derivatives gain importance in thermal paper application. In this study, a rapid, reliable and cost-effective method for identification and quantification of BPA, alternative color developers and related substances like sensitizers is presented based on HPLC separation coupled with diode array detection (DAD) and Corona charged aerosol detection (CAD). Quantification was performed with regard to the intended use of the substances in thermal papers. Besides traditional UV external calibration using reference standards, alternative quantification approaches, in particular UV chromophore concentration for BPS derivatives and CAD universal response technique for low-volatile color developers, were applied and compared in order to allow quantification without reference substances. A market analysis for intended used color developers and sensitizers was performed on thermal paper samples (n = 211) collected in Germany during 2018 and 2019. Pergafast 201 (in 41.7% of the samples) was the most common color developer with concentrations above 0.02 wt%, followed by BPA (36.0%), BPS (13.3%) and other BPS derivatives known as D8, D-90, BPS-MAE and TGSA, that are mainly present in adhesive labels. Sensitizers were determined in over 90% of the samples.

To study the relationship between exposure to airborne particles in a pulp and paper mill and markers of inflammation and coagulation in blood. Personal sampling of inhalable dust was performed for 72 subjects working in a Swedish pulp and paper mill. Stationary measurements were used to study concentrations of total dust, respirable dust, PM10 and PM2.5, the particle surface area and the particle number concentrations. Markers of inflammation, interleukins (IL-1b, IL-6, IL-8, and IL-10), C-reactive protein (CRP), serum amyloid A (SAA), and fibrinogen and markers of coagulation factor VIII, von Willebrand, plasminogen activator inhibitor, and D-dimer were measured in plasma or serum. Sampling was performed on the last day of the work free period of 5 days, before and after the shift the first day of work and after the shifts the second and third day. In a mixed model analysis, the relationship between particulate exposures and inflammatory markers was determined. Sex, age, smoking, and BMI were included as covariates. The average 8-h time-weighted average (TWA) air concentration levels of inhalable dust were 0.30 mg/m(3), range 0.005-3.3 mg/m(3). The proxies for average 8-h TWAs of respirable dust were 0.045 mg/m(3). Significant and consistent positive relations were found between several exposure metrics (PM 10, total and inhalable dust) and CRP, SAA and fibrinogen taken post-shift, suggesting a dose-effect relationship. This study supports a relationship between occupational particle exposure and established inflammatory markers, which may indicate an increased risk of cardiovascular disease. Funding Agencies|Swedish Research Council for Health, Working Life and Welfare [2006-0152]

We demonstrate the use of patterned aerosol adhesives to construct both planar and nonplanar 3D paper microfluidic devices. By spraying an aerosol adhesive through a metal stencil, the overall amount of adhesive used in assembling paper microfluidic devices can be significantly reduced. We show on a simple 4-layer planar paper microfluidic device that the optimal adhesive application technique and device construction style depends heavily on desired performance characteristics. By moderately increasing the overall area of a device, it is possible to dramatically decrease the wicking time and increase device success rates while also reducing the amount of adhesive required to keep the device together. Such adhesive application also causes the adhesive to form semi-permanent bonds instead of permanent bonds between paper layers, enabling single-use devices to be non-destructively disassembled after use. Nonplanar 3D origami devices also benefit from the semi-permanent bonds during folding, as it reduces the likelihood that unrelated faces may accidently stick together. Like planar devices, nonplanar structures see reduced wicking times with patterned adhesive application vs uniformly applied adhesive.

A microfluidic paper-based analytical device (μPAD) fabricated by wax printing was designed to assess occupational exposure to metal-containing aerosols. This method employs rapid digestion of particulate metals using microliters of acid added directly to a punch taken from an air sampling filter. Punches were then placed on a μPAD, and digested metals were transported to detection reservoirs upon addition of water. These reservoirs contained reagents for colorimetric detection of Fe, Cu, and Ni. Dried buffer components were used to set the optimal pH in each detection reservoir, while precomplexation agents were deposited in the channels between the sample and detection zones to minimize interferences from competing metals. Metal concentrations were quantified from color intensity images using a scanner in conjunction with image processing software. Reproducible, log-linear calibration curves were generated for each metal, with method detection limits ranging from 1.0 to 1.5 μg for each metal (i.e., total mass present on the μPAD). Finally, a standard incineration ash sample was aerosolized, collected on filters, and analyzed for the three metals of interest. Analysis of this collected aerosol sample using a μPAD showed good correlation with known amounts of the metals present in the sample. This technology can provide rapid assessment of particulate metal concentrations at or below current regulatory limits and at dramatically reduced cost.

Experiments were conducted to illustrate some of the challenges associated with measuring dynamic MDI aerosols. Experimental HFA-134a solution MDIs containing 8 or 20% ethanol were measured using the Andersen cascade impactor using three different inlets. It was demonstrated that the size distribution of MDI aerosols changes substantially during the measurement process. The measured size distribution was shown to be dependent on the degree of evaporation that has occurred prior to size measurement. Additionally, the degree of evaporation prior to measurement also influences the number of modes present in the measured size distribution. While MDI aerosols appeared to have a separate large particle mode when measured using the U.S. Pharmacopeial induction port ("USP inlet"; [U.S. Pharmacopeia, 1996. Physical tests and determinations601aerosols, metered dose inhalers, and dry powders. Pharmacopeial Forum 22, pp. 3065-3095]), the aerosols were shown to be monomodal when measured using a large volume inlet. The apparent large particle mode observed with the USP inlet seem rather to be droplets from the same monomodal distribution that have not fully evaporated. The complex interaction of the MDI plume and inlet configuration was described. Inlet design was shown to influence inlet deposition, measured particle size, and even deposition in the actuator mouthpiece. Inlet deposition was shown to be highly size-dependent with large droplets being collected more efficiently than smaller droplets.

One limitation in the growing field of ambient or direct analysis methods is reduced selectivity caused by the elimination of chromatographic separations prior to mass spectrometric analysis. We explored the use of high-field asymmetric waveform ion mobility spectrometry (FAIMS), an ambient pressure ion mobility technique, to separate the closely related opiate isomers of morphine, hydromorphone, and norcodeine. These isomers cannot be distinguished by tandem mass spectrometry. Separation prior to MS analysis is, therefore, required to distinguish these compounds, which are important in clinical chemistry and toxicology. FAIMS was coupled to a triple quadrupole mass spectrometer, and ionization was performed using either a pneumatically assisted heated electrospray ionization source (H-ESI) or paper spray, a direct analysis method that has been applied to the direct analysis of dried blood spots and other complex samples. We found that FAIMS was capable of separating the three opiate structural isomers using both H-ESI and paper spray as the ionization source.

Ewapower Ltd in Pietarsaari, Finland produces pellets from paper and plastic waste for burning. During 1998 and 1999, several measurements were made to determine the dust, particle, microbe and endotoxin concentrations, and also the noise level in the hall where the waste is received and pre-crushed. The noise level exceeded the Finnish recommended level of 85 dBA. The dust and the particle concentrations were low, but the microbe concentrations, especially in the summer and in the autumn, were at a level which may be harmful to health. The total concentration of microbes (both dead and alive) was high - approximately 4.8 million particles m-3. The concentrations of endotoxins was high in summer and in autumn, from 340 to 1000 ng m-3 and exceeded recommended values. In the winter, the concentration of the endotoxin was lower, ranging between 4.7 and 33 ng m-3.

The exponentially decaying acoustic pressure of scattered surface acoustic waves (SAWs) at the contact line of a liquid film pinned to filter paper is shown to sustain a high curvature conic tip with micron-sized modulations whose dimension grows exponentially from the tip. The large negative capillary pressure in the film, necessary for offsetting the large positive acoustic pressure at the contact line, also creates significant negative hydrodynamic pressure and robust wicking action through the paper. An asymptotic analysis of this intricate pressure matching between the quasistatic conic film and bulk drop shows that the necessary SAW power to pump liquid from the filter paper and aerosolize, expressed in terms of the acoustic pressure scaled by the drop capillary pressure, grows exponentially with respect to twice the acoustic decay constant multiplied by the drop length, with a universal preexponential coefficient. Global rapid aerosolization occurs at a SAW power twice as high, beyond which the wicking rate saturates.

Human exposure to particulate matter (PM) air pollution has been linked with respiratory, cardiovascular, and neurodegenerative diseases, in addition to various cancers. Consistent among all of these associations is the hypothesis that PM induces inflammation and oxidative stress in the affected tissue. Consequently, a variety of assays have been developed to quantify the oxidative activity of PM as a means to characterize its ability to induced oxidative stress. The vast majority of these assays rely on high-volume, fixed-location sampling methods due to limitations in assay sensitivity and detection limit. As a result, our understanding of how personal exposure contributes to the intake of oxidative air pollution is limited. To further this understanding, we present a microfluidic paper-based analytical device (μPAD) for measuring PM oxidative activity on filters collected by personal sampling. The μPAD is inexpensive to fabricate and provides fast and sensitive analysis of aerosol oxidative activity. The oxidative activity measurement is based on the dithiothreitol assay (DTT assay), uses colorimetric detection, and can be completed in the field within 30 min following sample collection. The μPAD assay was validated against the traditional DTT assay using 13 extracted aerosol samples including urban aerosols, biomass burning PM, cigarette smoke, and incense smoke. The results showed no significant differences in DTT consumption rate measured by the two methods. To demonstrate the utility of the approach, personal samples were collected to estimate human exposures to PM from indoor air, outdoor air on a clean day, and outdoor air on a wildfire-impacted day in Fort Collins, CO. Filter samples collected on the wildfire day gave the highest oxidative activity on a mass normalized basis, whereas typical ambient background air showed the lowest oxidative activity.

Previous studies of paper machine operators have to a large extent focused on endotoxins as a possible health hazard, but not culturable micro-organisms (MOs).Based on exposure assessment in 11 paper mills workers exposed to culturable bio-aerosols were grouped in three exposure groups. 781 exposed and 285 unexposed workers completed a questionnaire that provided data pertaining to infections and associated symptoms.Concentrations of culturable bacteria in process waters varied in the range 10(4)-10(6) colony forming units (cfu)/ml, and in bio-aerosols concentrations varied typically in the range 10(4)--10(5) cfu/m3. Operators exposed to bio-aerosols reported higher cumulative incidence of symptoms associated with infections compared to the reference population (ORs = 1.7-5.9), and the group of highest exposed workers reported higher cumulative incidence than the group of lowest exposed (ORs = 1.2-3.6).Exposure to bio-aerosols containing culturable MOs may induce symptoms associated with infections among operators in paper mills.

Airborne particulate matter (PM) pollution significantly impacts human health, but the cellular mechanisms of PM-induced toxicity remain poorly understood. A leading hypothesis on the effects of inhaled PM involves the generation of cellular oxidative stress. To investigate PM-induced oxidative stress, analytical methods have been developed to study the chemical oxidation of dithiothreitol (DTT) in the presence of PM. Although DTT readily reacts with several forms of reactive oxygen species, this molecule is not endogenously produced in biological systems. Glutathione (GSH), on the other hand, is an endogenous antioxidant that is produced throughout the body and is directly involved in combating oxidative stress in the lungs and other tissues. We report here a new method for measuring aerosol oxidative activity that uses silver nanoparticle (AgNP) aggregation coupled to glutathione (GSH) oxidation in a paper-based analytical device. In this assay, the residual reduced GSH from the oxidation of reduced GSH to its disulfide induces the aggregation of AgNPs on a paper-based analytical device, which produces a reddish-brown product. Two methods for aerosol oxidative reactivity are presented: one based on change in color intensity using a traditional paper-based techniques and one based on the length of the color product formed using a distance-based device. These methods were validated against traditional spectroscopic assays for DTT and GSH that employ Elman's reagent. No significant difference was found between the levels measured by all three GSH methods (our two paper-based devices and the traditional method) at the 95% confidence level. PM reactivity towards GSH was less than towards DTT most likely due to the difference in the oxidation potential between the two molecules.

The incidence of microbes in the nasal cavities of workers in three paper and board mills was investigated. A total of 234 persons exposed to microbial aerosols and splashes from paper machine wires and debarker drums formed the exposed group. The control group consisted of 294 workers from the dry working areas: the winding and packing sections. Chi-square analysis was used to test the differences in the frequency of microbial incidence and various symptoms between the exposed and control groups. The nasal cavities of many workers, particularly workers in the debarkers, proved to be contaminated by Klebsiella pneumoniae, other coliforms, yeasts, and molds; usually only one microbe was involved, but sometimes two or several species were found. Nasal bacteria and yeasts were largely derived from the mill and debarker air; the microbes in the air came mainly from process waters. Lack of association of nasopharyngeal symptoms with either exposure to aerosols or nasal microbial contamination was interpreted as an indication of host defenses that were adequate to protect workers from harmful microbial colonization in paper mill environments.

The collection efficiency of Whatman 41 filter paper has been determined using submicron test aerosols of monodispersed polystyrene latex. Measurements were made over a velocity range of 12 to 195 fpm, using aerosols with diameters of 0.088, 0.188, 0.264, 0.365, and 0.557 mu . For sizes less than 0.557 mu , well-developed efficiency minima occur in the velocity range of 20 to 30 fpm. In no case was the efficiency found to be below 70%. At 195 fpm, the efficiency was essentially size-independent. (auth)

A study of the forward collection efficiencies of paper-coated glass and copper cylinders (diameters of 7.5 and 4.0 cm) was conducted in a wind tunnel in which the flow was turbulent. Dibutyl phthalate droplets of MMD 1.3 microns were collected in air-flow velocities of 16.8, 12, and 8.3 mph. Deposition by inertial impaction was precluded by selection of these particle sizes, wind velocity, and cylinder size. The forward collection efficiencies were less than 1% in all cases (greater for the paper-coated glass cylinders than for the paper-coated copper). In general, the forward collection efficiency increased with the reciprocal of the cylinder diameter and was greater at 16.8 mph than at 12.0 and 8.3 mph. At the turbulence intensities used in this work (0.5%, 1.8%, and 4.7%), intensity of turbulence had no effect on forward collection efficiency.

IPC-1478 filter paper efficiency was evaluated using polystyrene latex and dioctyl phthalate (DOP aerosols). Efficiency was measured as a function of particle size, filtration velocity, and filter mass loading. Experimental results of 0.557-µm and larger particle sizes indicate that this medium has limited effectiveness under high-velocity and high-loading conditions. Differences in efficiency were observed when this medium was tested with solid and liquid aerosols.

Oil mist can be efficiently collected on filter paper or by an electrostatic precipitator. Samples containing 0.05 mg of oil can be accurately determined by ultraviolet spectrophotometry. Gross amounts of sample contaminants, such as soil, water, and pipe scale, can be tolerated without appreciable loss in accuracy. Petroleum distillate vapor is efficiently collected on silica gel or in a midget bubbler containing chloroform. Maximum collection efficiency is achieved at sampling rates not exceeding 100 cc/min. Samples containing as little as 0.5 mg in 10 ml of chloroform or ethanol may be determined by spectrophotometry. With both oil and petroleum distillate determinations, it is necessary to obtain a sample of the particular product in question in order to construct a standard spectrophotometric curve.