HBM4EU E-waste study: Assessing persistent organic pollutants in blood, silicone wristbands, and settled dust among E-waste recycling workers in Europe.

E-waste recycling is an increasingly important activity that contributes to reducing the burden of end-of-life electronic and electrical apparatus and allows for the EU's transition to a circular economy. This study investigated the exposure levels of selected persistent organic pollutants (POPs) in workers from e-waste recycling facilities across Europe. The concentrations of seven polychlorinated biphenyls (PCBs) and eight polybrominated diphenyl ethers (PBDEs) congeners were measured by GC-MS. Workers were categorized into five groups based on the type of e-waste handled and two control groups. Generalized linear models were used to assess the determinants of exposure levels among workers. POPs levels were also assessed in dust and silicone wristbands (SWB) and compared with serum. Four PCB congeners (CB 118, 138, 153, and 180) were frequently detected in serum regardless of worker's category. With the exception of CB 118, all tested PCBs were significantly higher in workers compared to the control group. Controls working in the same company as occupationally exposed (Within control group), also displayed higher levels of serum CB 180 than non-industrial controls with no known exposures to these chemicals (Outwith controls) (p < 0.05). BDE 209 was the most prevalent POP in settled dust (16 µg/g) and SWB (220 ng/WB). Spearman correlation revealed moderate to strong positive correlations between SWB and dust. Increased age and the number of years smoked cigarettes were key determinants for workers exposure. Estimated daily intake through dust ingestion revealed that ΣPCB was higher for both the 50th (0.03 ng/kg bw/day) and 95th (0.09 ng/kg bw/day) percentile exposure scenarios compared to values reported for the general population. This study is one of the first to address the occupational exposure to PCBs and PBDEs in Europe among e-waste workers through biomonitoring combined with analysis of settled dust and SWB. Our findings suggest that e-waste workers may face elevated PCB exposure and that appropriate exposure assessments are needed to establish effective mitigation strategies.

Plasma glycoproteomics delivers high-specificity disease biomarkers by detecting site-specific glycosylation abnormalities.

INTRODUCTION: The human plasma glycoproteome holds enormous potential to identify personalized biomarkers for diagnostics. Glycoproteomics has matured into a technology for plasma N-glycoproteome analysis but further evolution towards clinical applications depends on the clinical validity and understanding of protein- and site-specific glycosylation changes in disease. OBJECTIVES: Here, we exploited the uniqueness of a patient cohort of genetic defects in well-defined glycosylation pathways to assess the clinical applicability of plasma N-glycoproteomics. METHODS: Comparative glycoproteomics was performed of blood plasma from 40 controls and 74 patients with 13 different genetic diseases that impact the protein N-glycosylation pathway. Baseline glycosylation in healthy individuals was compared to reference glycome and intact transferrin protein mass spectrometry data. Use of glycoproteomics data for biomarker discovery and sample stratification was evaluated by multivariate chemometrics and supervised machine learning. Clinical relevance of site-specific glycosylation changes were evaluated in the context of genetic defects that lead to distinct accumulation or loss of specific glycans. Integrated analysis of site-specific glycoproteome changes in disease was performed using chord diagrams and correlated with intact transferrin protein mass spectrometry data. RESULTS: Glycoproteomics identified 191 unique glycoforms from 58 unique peptide sequences of 34 plasma glycoproteins that span over 3 magnitudes of abundance in plasma. Chemometrics identified high-specificity biomarker signatures for each of the individual genetic defects with better stratification performance than the current diagnostic standard method. Bioinformatic analyses revealed site-specific glycosylation differences that could be explained by underlying glycobiology and protein-intrinsic factors. CONCLUSION: Our work illustrates the strong potential of plasma glycoproteomics to significantly increase specificity of glycoprotein biomarkers with direct insights in site-specific glycosylation changes to better understand the glycobiological mechanisms underlying human disease.

Impact of infection on proteome-wide glycosylation revealed by distinct signatures for bacterial and viral pathogens.

Mechanisms of infection and pathogenesis have predominantly been studied based on differential gene or protein expression. Less is known about posttranslational modifications, which are essential for protein functional diversity. We applied an innovative glycoproteomics method to study the systemic proteome-wide glycosylation in response to infection. The protein site-specific glycosylation was characterized in plasma derived from well-defined controls and patients. We found 3862 unique features, of which we identified 463 distinct intact glycopeptides, that could be mapped to more than 30 different proteins. Statistical analyses were used to derive a glycopeptide signature that enabled significant differentiation between patients with a bacterial or viral infection. Furthermore, supported by a machine learning algorithm, we demonstrated the ability to identify the causative pathogens based on the distinctive host blood plasma glycopeptide signatures. These results illustrate that glycoproteomics holds enormous potential as an innovative approach to improve the interpretation of relevant biological changes in response to infection.

Reply to Viner, A.; Ayrey, S. Comment on "Scheepers et al. Comparative Performance Testing of Respirator versus Surgical Mask Using a Water Droplet Spray Model. Int. J. Environ. Res. Public Health 2021, 18, 1599".

The response to our publication by Andrew Viner and Stewart Ayrey is much appreciated [...].

Determination of cytotoxicity following oxidative treatment of pharmaceutical residues in wastewater.

Pharmaceutical residues are released in the aquatic environment due to incomplete removal from wastewater. With the presence of multiple chemicals in sewage waters, contaminants may adversely affect the effectiveness of a wastewater treatment plant (WWTP). In certain cases, discharged metabolites are transformed back into their pristine structure and become bioactive again. Other compounds are persistent and can withstand conventional wastewater treatment. When WWTP effluents are released in surface waters, pristine and persistent chemicals can affect the aquatic environment. To complement WWTPs and circumvent incomplete removal of unwanted chemicals or pharmaceuticals, on-site wastewater treatment can contribute to their removal. Advanced oxidation processes (AOPs) are very powerful techniques for the abatement of pharmaceuticals, however, under certain circumstances reactive toxic by-products can be produced. We studied the application of on-site AOPs in a laboratory setting. It is expected that treatment at the contamination source can eliminate the worst polluters. Thermal plasma and UV/H2O2 oxidation were applied on simulation matrices, Milli-Q and synthetic sewage water spiked with 10 different pharmaceuticals in a range of 0.1 up to 2400 µg/L. In addition, untreated end-of-pipe hospital effluent was also subjected to oxidative treatment. The matrices were activated for 180 min and added to cultured HeLa cells. The cells were 24 h and 48 h exposed at 37 °C and subsequently markers for oxidative stress and viability were measured. During the UV/H2O2 treatment periods no toxicity was observed. After thermal plasma activation of Milli-Q water (150 and 180 min) toxicity was observed. Direct application of thermal plasma treatment in hospital sewage water caused elimination of toxic substances. The low cytotoxicity of treated pharmaceutical residues is likely to become negligible if plasma pre-treated on-site wastewater is further diluted with other sewage water streams, before reaching the WWTP. Our study suggests that AOPs may be promising technologies to remove a substantial portion of pharmaceutical components by degradation at the source. Further studies will have to be performed to verify the feasibility of upscaling this technology from the benchtop to practice.

Collection of human and environmental data on pesticide use in Europe and Argentina: Field study protocol for the SPRINT project.

Current farm systems rely on the use of Plant Protection Products (PPP) to secure high productivity and control threats to the quality of the crops. However, PPP use may have considerable impacts on human health and the environment. A study protocol is presented aiming to determine the occurrence and levels of PPP residues in plants (crops), animals (livestock), humans and other non-target species (ecosystem representatives) for exposure modelling and impact assessment. To achieve this, we designed a cross-sectional study to compare conventional and organic farm systems across Europe. Environmental and biological samples were/are being/will be collected during the 2021 growing season, at 10 case study sites in Europe covering a range of climate zones and crops. An additional study site in Argentina will inform the impact of PPP use on growing soybean which is an important European protein-source in animal feed. We will study the impact of PPP mixtures using an integrated risk assessment methodology. The fate of PPP in environmental media (soil, water and air) and in the homes of farmers will be monitored. This will be complemented by biomonitoring to estimate PPP uptake by humans and farm animals (cow, goat, sheep and chicken), and by collection of samples from non-target species (earthworms, fish, aquatic and terrestrial macroinvertebrates, bats, and farm cats). We will use data on PPP residues in environmental and biological matrices to estimate exposures by modelling. These exposure estimates together with health and toxicity data will be used to predict the impact of PPP use on environment, plant, animal and human health. The outcome of this study will then be integrated with socio-economic information leading to an overall assessment used to identify transition pathways towards more sustainable plant protection and inform decision makers, practitioners and other stakeholders regarding farming practices and land use policy.

Thermal plasma activation and UV/H2O2 oxidative degradation of pharmaceutical residues.

The aquatic environment becomes increasingly contaminated by anthropogenic pollutants such as pharmaceutical residues. Due to poor biodegradation and continuous discharge of persistent compounds in sewage water samples, pharmaceutical residues might end up in surface waters when not removed. To minimize this pollution, onsite wastewater treatment techniques might complement conventional waste water treatment plants (WWTPs). Advanced oxidation processes are useful techniques, since reactive oxygen species (ROS) are used for the degradation of unwanted medicine residues. In this paper we have studied the advanced oxidation in a controlled laboratory setting using thermal plasma and UV/H2O2 treatment. Five different matrices, Milli-Q water, tap water, synthetic urine, diluted urine and synthetic sewage water were spiked with 14 pharmaceuticals with a concentration of 5 µg/L. All compounds were reduced or completely decomposed by both 150 W thermal plasma and UV/H2O2 treatment. Additionally, also hospital sewage water was tested. First the concentrations of 10 pharmaceutical residues were determined by liquid chromatography mass spectrometry (LC-MS/MS). The pharmaceutical concentration ranged from 0.08 up to 2400 µg/L. With the application of 150 W thermal plasma or UV/H2O2, it was found that overall pharmaceutical degradation in hospital sewage water were nearly equivalent to the results obtained in the synthetic sewage water. However, based on the chemical abatement kinetics it was demonstrated that the degree of degradation decreases with increasing matrix complexity. Since reactive oxygen and nitrogen species (RONS) are continuously produced, thermal plasma treatment has the advantage over UV/H2O2 treatment.

Comparative Performance Testing of Respirator versus Surgical Mask Using a Water Droplet Spray Model.

BACKGROUND: During the SARS-CoV-2 pandemic, there was shortage of the standard respiratory protective equipment (RPE). The aim of this study was to develop a procedure to test the performance of alternative RPEs used in the care of COVID-19 patients. METHODS: A laboratory-based test was developed to compare RPEs by total inward leakage (TIL). We used a crossflow nebulizer to produce a jet spray of 1-100 µm water droplets with a fluorescent marker. The RPEs were placed on a dummy head and sprayed at distances of 30 and 60 cm. The outcome was determined as the recovery of the fluorescent marker on a membrane filter placed on the mouth of the dummy head. RESULTS: At 30 cm, a type IIR surgical mask gave a 17.7% lower TIL compared with an FFP2 respirator. At 60 cm, this difference was similar, with a 21.7% lower TIL for the surgical mask compared to the respirator. When adding a face shield, the TIL at 30 cm was further reduced by 9.5% for the respirator and 16.6% in the case of the surgical mask. CONCLUSIONS: A safe, fast and very sensitive test method was developed to assess the effectiveness of RPE by comparison under controlled conditions.

Assessment of exposure of gas station attendants in Sri Lanka to benzene, toluene and xylenes.

Exposure to benzene, toluene and p-, m-, o-xylene (BTX) was studied in 29 gas station attendants and 16 office workers in Sri Lanka. The aim of this study was to assess the exposure level and identify potential exposure mitigating measures. Pre- and post-shift samples of end-exhaled air were collected and analysed for BTX on a thermal desorption gas chromatography mass spectrometry system (TD-GC-MS). Urine was collected at the same timepoints and analysed for a metabolite of benzene, S-phenyl mercapturic acid (SPMA), using liquid chromatography-mass spectrometry (LC-MS). Environmental exposure was measured by personal air sampling and analysed by gas chromatography flame ionization detection (GC-FID). Median (range) breathing zone air concentrations were 609 (65.1-1960) µg/m3 for benzene and 746 (<5.0-2770) µg/m3 for toluene. Taking into account long working hours, 28% of the measured exposures exceeded the ACGIH threshold limit value (TLV) for an 8-h time-weighted average of 1.6 mg/m3 for benzene. Xylene isomers were not detected. End-exhaled air concentrations were significantly increased for gas station attendants compared to office workers (p < 0.005). The difference was 1-3-fold in pre-shift and 2-5-fold in post-shift samples. The increase from pre-to post-shift amounted to 5-15-fold (p < 0.005). Pre-shift BTX concentrations in end-exhaled air were higher in smokers compared to non-smokers (p < 0.01). Exposure due to self-reported fuel spills was related to enhanced exhaled BTX (p < 0.05). The same was found for sleeping at the location of the gas station between two work-shifts. Benzene in end-exhaled air was moderately associated with benzene in the breathing zone (r = 0.422; p < 0.001). Median creatinine-corrected S-phenyl mercapturic acid (SPMA) was similar in pre- and post-shift (2.40 and 3.02 µg/g) in gas station attendants but increased in office workers (from 0.55 to 1.07 µg/g). In conclusion, working as a gas station attendant leads to inhalation exposure and occasional skin exposure to BTX. Smoking was identified as the most important co-exposure. Besides taking preventive measure to reduce exposure, the reduction of working hours to 40 h per week is expected to decrease benzene levels below the current TLV.

Intrusion of chlorinated hydrocarbons and their degradation products from contaminated soil. Measurement of indoor air quality and biomonitoring by analysis of end-exhaled air.

A historic soil contamination of chlorinated hydrocarbons from a former dry cleaning shop caused intrusion of vapors into a building currently used as bookshop. The aim of this study was to determine the indoor air quality and the uptake of soil contaminants and their degradation products. Samples of indoor air were collected over one week in the warm and one week in the cold season. Pre-shift and post-shift samples of end-exhaled air were collected from two employees. Chlorinated hydrocarbons were analyzed in indoor air and exhaled air samples using thermal desorption gas chromatography mass spectrometry (TD-GC-MS). Tetrachloroethylene (PER), and its degradation products trichloroethylene (TRI), 1,1-dichloroethylene (1,1-DCE), 1,2-cis-dichloroethylene (1,2-cis-DCE), 1,2-trans-dichloroethylene (1,2-trans-DCE), methylene chloride (MC) and vinyl chloride (VC) were determined in ambient air. PER was the prime contaminant with a week average (±sd) of 805.2 ±â€¯598.6 µg/m3 in June 2016 and 1031 ±â€¯499.3 µg/m3 in December 2017. MC, 1,2-cis-DCE and TRI were detected at concentrations below 2.3 µg/m3. 1,1-DCE and VC were not detected. In exhaled air PER, 1,1-DCE, and MC were detected in both June and December, whereas TRI, 1,2-cis-DCE and 1,2-trans-DCE were only detected on one or two days in the cold season. VC was not detected in exhaled air. For PER, the mean concentrations (±sd) in end-exhaled air increased from a five days (Mon-Fri) average pre-shift value of 22.2 ±â€¯8.0 to a post-shift value of 52.6 ±â€¯15.5 ng/L in the male shop owner (p < 0.01) and in the female cashier these values were 26.0 ±â€¯3.6 and 63.6 ±â€¯12.7 ng/L, respectively (p < 0.01). Intrusion of chlorinated soil contaminants resulted in contamination of indoor air above the current accepted indoor air level for PER of 250 µg/m3. For PER in end-exhaled air an accumulation over the workweek was not observed.

Changes in Work Practices for Safe Use of Formaldehyde in a University-Based Anatomy Teaching and Research Facility.

Anatomy teaching and research relies on the use of formaldehyde (FA) as a preservation agent for human and animal tissues. Due to the recent classification of FA as a carcinogen, university hospitals are facing a challenge to (further) reduce exposure to FA. The aim of this study was to reduce exposure to FA in the anatomy teaching and research facility. Workers participated in the development of improved work practices, both technical and organizational solutions. Over a period of 6 years mitigating measures were introduced, including improvement of a down-flow ventilation system, introduction of local exhaust ventilation, collection of drain liquid from displayed specimens in closed containers and leak prevention. Furthermore, some organizational changes were made to reduce the number of FA peak exposures. Stationary and personal air sampling was performed in three different campaigns to assess the effect of these new work practices on inhalation exposure to FA. Samples were collected over 8 h (full shift) and 15 min (task-based) to support mitigation of exposure and improvement of work practices. Air was collected on an adsorbent coated with 2,4-dinitrophenylhydrazine (DNPH) and analyzed by HPLC-UV. Geometric mean (GM) concentrations of FA in the breathing zone over a work-shift were 123 µg/m³ in 2012 and 114 µg/m³ in 2014, exceeding the workplace standard of 150 µg/m³ (8 h time-weighted average, TWA) on 46% of the workdays in 2012 and 38% of the workdays in 2014. This exposure was reduced to an average of 28.8 µg/m³ in 2017 with an estimated probability of exceeding the OEL of 0.6%. Task-based measurements resulted in a mean peak exposures of 291 µg/m³ in 2012 (n = 19) and a mean of 272 µg/m³ in 2014 (n = 21), occasionally exceeding the standard of 500 µg/m³ (15 min TWA), and were reduced to a mean of 88.7 µg/m³ in 2017 (n = 12) with an estimated probability of exceeding the OEL of 1.6%.

A comprehensive full factorial LC-MS/MS proteomics benchmark data set.

An important prerequisite for the development and benchmarking of novel analysis methods is a well-designed comprehensive LC-MS/MS data set. Here, we present our data set consisting of 59 LC-MS/MS analyses of 50 protein samples extracted individually from Escherichia coli K12 and spiked with different concentrations of bovine carbonic anhydrase II and/or chicken ovalbumin, according to a 2 × 3 full factorial design. Using the well-annotated and commonly used E. coli proteome as the sample background ensures that the complexity of the data is on a par with most current proteomic analyses. Data were acquired over a 2-month period using multiple reversed-phase columns and instrument calibrations to include real-life challenges faced when analyzing large proteomics data sets. Moreover, so-called "ground truth" data, comprised by LC-MS/MS measurements of the pure spikes are included in the data set. The current manuscript elaborates this comprehensive benchmark data set for future development and evaluation of analysis methods and software.

Pinpointing biomarkers in proteomic LC/MS data by moving-window discriminant analysis.

The identification of differential patterns in data originating from combined measurement techniques such as LC/MS is pivotal to proteomics. Although "shotgun proteomics" has been employed successfully to this end, this method also has severe drawbacks, because of its dependence on largely untargeted MS/MS sequencing and databases for statistical analyses. Alternatively, several MS-signal-based (MS/MS-independent) methods have been published that are mainly based on (univariate) Student's t-tests. Here, we present a more robust multivariate alternative employing linear discriminant analysis. Like the t-test-based methods, it is applied directly to LC/MS data, instead of using MS/MS measurements. We demonstrate the method on a number of simulated data sets, as well as on a spike-in LC/MS data set, and show its superior performance over t-tests.