Chlorinated organophosphate esters in Irish waste foams and fabrics: Concentrations, preliminary assessment of temporal trends and evaluation of the impact of a concentration limit value.

Concentrations of the chlorinated organophosphate esters (Cl-OPEs): tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) were measured in 273 waste synthetic foam and fabric articles collected in Ireland between 2019 and 2020. Articles examined comprised: polystyrene building insulation foam, as well as foam fillings and fabric coverings from furniture, mattresses, end-of-life vehicles, curtains, and carpets. Cl-OPEs were also measured in 156 samples from the same categories (except for building insulation foam) collected in 2015-16. Concentrations of TCIPP and TDCIPP in most samples exceeded those of TCEP; with those of TCIPP and TDCIPP generally and for some waste categories significantly (p < 0.05) higher in samples collected in 2019-20. Given potential future restrictions on use of these Cl-OPEs, we identified articles containing concentrations that exceeded 1000 mg/kg, in line with a similar limit that at the time of sample collection existed for some brominated flame retardants within the European Union. In 2019-20, 82 articles contained at least one Cl-OPE above 1000 mg/kg, with at least one article exceeding this concentration in each waste category examined. By comparison, only 28 samples collected in 2015-16, contained at least one Cl-OPE >1000 mg/kg, and articles exceeding this concentration were restricted to furniture and mattress foam, along with foams and fabrics from end-of-life vehicles. In the event of the introduction of such a limit on Cl-OPE concentrations in waste, it will result in 7200 t/year of such waste (24 % of the total) being rendered unrecyclable, while removing 98 % of the estimated ∼147,000 kg/year of Cl-OPEs from the recycling stream.

Halogenated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and preliminary assessment of temporal trends.

Halogenated flame retardants (HFRs) were measured in 470 waste plastic articles from Ireland between 2019 and 2020. We identified articles containing concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and tetrabromobisphenol-A (TBBP-A) exceeding European Union limits. Enforcement of existing limits of 1000 mg/kg will render an estimated 3.1% (2800 t) of articles in the waste categories studied unrecyclable, increasing to: 4.0, 4.9, and 5.6% if limits were reduced to 500, 200, and 100 mg/kg respectively. Meanwhile, enforcing limits of 1,000, 500, 200, and 100 mg/kg will respectively remove 78, 82, 84, and 85% of PBDEs, HBCDD, and TBBP-A present in such waste. Other FRs targeted were detected infrequently and predominantly at very low concentrations. However, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) was detected in 3 display/IT product samples at 14,000 to 32,000 mg/kg, indicating elevated concentrations of FRs used as alternatives to PBDEs and HBCDD, will likely increase in future. Comparison with data for Ireland in 2015-16, revealed concentrations and exceedances of limits for PBDEs, HBCDD, and TBBP-A were similar or have declined. For end-of-life vehicle fabrics and foams, HBCDD and ΣPBDE concentrations declined significantly (p < 0.05) since 2015-16. Moreover, ΣPBDE concentrations in waste small domestic appliances are significantly lower in 2019-20, with a similarly significant decline for TBBP-A in waste IT and telecommunications articles. In contrast, HBCDD concentrations in waste extruded polystyrene increased significantly between 2015-16 and 2019-20. For other waste categories studied, no statistically significant temporal trends are evident (p > 0.05). Fewer samples exceeded PBDE and HBCDD limits in 2019-20 (7.8%) than 2015-16 (8.7%), while exceedances for TBBP-A fell from 2.4% in 2015-16 to 0.57% in 2019-20. While comparison between the 2015-16 and 2019-20 datasets provide a preliminary indication of changes, further monitoring is required if the impact of legislation designed to eliminate HFRs from the waste stream is to be fully evaluated.

Exposure assessment using human biomonitoring for glyphosate and fluroxypyr users in amenity horticulture.

BACKGROUND: Pesticides and their potential adverse health effects are of great concern and there is a dearth of knowledge regarding occupational exposure to pesticides among amenity horticulturalists. OBJECTIVE: This study aims to measure occupational exposures to amenity horticuturalists using pesticides containing the active ingredients, glyphosate and fluroxypyr by urinary biomonitoring. METHODS: A total of 40 work tasks involving glyphosate and fluroxypyr were surveyed over the period of June - October 2015. Workers used a variety of pesticide application methods; manual knapsack sprayers, controlled droplet applicators, pressurised lance applicators and boom sprayers. Pesticide concentrations were measured in urine samples collected pre and post work tasks using liquid chromatography tandem mass spectrometry (LC-MS/MS). Differences in pesticide urinary concentrations pre and post work task, and across applications methods were analysed using paired t-tests and linear regression. RESULTS: Pesticide urinary concentrations were higher than those reported for environmental exposures and comparable to those reported in some agricultural studies. Log-transformed pesticide concentrations were statistically significantly higher in post-work samples compared to those in pre-work samples (paired t-test, p<0.001; for both µgL-1 and µmol/mol creatinine). Urinary pesticide concentrations in post-work samples had a geometric mean (geometric standard deviation) of 0.66 (1.11) µgL-1 for glyphosate and 0.29 (1.69) µgL-1 for fluroxypyr. Linear regression revealed a statistically significant positive association to exist between the time-interval between samples and the log-transformed adjusted (i.e. post- minus pre-task) pesticide urinary concentrations (ß=0.0039; p<0.0001). CONCLUSION: Amenity horticulturists can be exposed to pesticides during tasks involving these products. Further research is required to evaluate routes of exposure among this occupational group.

Using PM2.5 concentrations to estimate the health burden from solid fuel combustion, with application to Irish and Scottish homes.

BACKGROUND: This study estimates the potential population health burden from exposure to combustion-derived particulate air pollution in domestic settings in Ireland and Scotland. METHODS: The study focused on solid fuel combustion used for heating and the use of gas for cooking. PM2.5 (particulate matter with an aerodynamic diameter < 2.5 µm) was used as the pollutant mixture indicator. Measured PM2.5 concentrations in homes using solid fuels were adjusted for other sources of PM2.5 by subtracting PM2.5 concentrations in homes using gas for cooking but not solid fuel heating. Health burden was estimated for exposure indoors 6 pm - midnight, or all day (24-hour), by combining estimated attributable annual PM2.5 exposures with (i) selected epidemiological functions linking PM2.5 with mortality and morbidity (involving some re-scaling from PM10 to PM2.5, and adjustments 'translating' from concentrations to exposures) and (ii) on the current population exposed and background rates of morbidity and mortality. RESULTS: PM2.5 concentrations in coal and wood burning homes were similar to homes using gas for cooking, used here as a baseline (mean 24-hr PM2.5 concentrations 8.6 µg/m3) and so health impacts were not calculated. Concentrations of PM2.5 in homes using peat were higher (24-hr mean 15.6 µg/m3); however, health impacts were calculated for the exposed population in Ireland only; the proportion exposed in Scotland was very small. The assessment for winter evening exposure (estimated annual average increase of 2.11 µg/m3 over baseline) estimated 21 additional annual cases of all-cause mortality, 55 of chronic bronchitis, and 30,100 and 38,000 annual lower respiratory symptom days (including cough) and restricted activity days respectively. CONCLUSION: New methods for estimating the potential health burden of combustion-generated pollution from solid fuels in Irish and Scottish homes are provided. The methodology involves several approximations and uncertainties but is consistent with a wider movement towards quantifying risks in PM2.5 irrespective of source. Results show an effect of indoor smoke from using peat (but not wood or coal) for heating and cooking; but they do not suggest that this is a major public health issue.

Validation of the inhalable dust algorithm of the Advanced REACH Tool using a dataset from the pharmaceutical industry.

As it is often difficult to obtain sufficient numbers of measurements to adequately characterise exposure levels, occupational exposure models may be useful tools in the exposure assessment process. This study aims to refine and validate the inhalable dust algorithm of the Advanced REACH Tool (ART) to predict airborne exposure of workers in the pharmaceutical industry. The ART was refined to reflect pharmaceutical situations. Largely task based workplace exposure data (n = 192) were collated from a multinational pharmaceutical company with exposure levels ranging from 5 × 10(-5) to 12 mg m(-3). Bias, relative bias and uncertainty around geometric mean exposure estimates were calculated for 16 exposure scenarios. For 12 of the 16 scenarios the ART geometric mean exposure estimates were lower than measured exposure levels with on average, a one-third underestimation of exposure (relative bias -32%). For 75% of the scenarios the exposure estimates were, within the 90% uncertainty factor of 4.4, as reported for the original calibration study, which may indicate more uncertainty in the ART estimates in this industry. While the uncertainty was higher than expected this is likely due to the limited number of measurements per scenario, which were largely derived from single premises.

Refinement and validation of an exposure model for the pharmaceutical industry.

OBJECTIVES: Assessment of worker's exposure is becoming increasingly critical in the pharmaceutical industry as drugs of higher potency are being manufactured. The batch nature of operations often makes it difficult to obtain sufficient numbers of exposure measurements and occupational exposure models may be useful tools in the exposure assessment process. This paper aims to describe further refinement and validation of an existing deterministic occupational exposure model to predict airborne exposure of workers in this industry. METHODS: Workplace exposure assessment data (n = 381) containing all the contextual information required for the exposure model were collated from a multinational pharmaceutical company. The measured exposure levels ranged from 5 × 10⁻7 to 200 mg m⁻³ for largely task based samples, and included a range of handling activities, local control measures and abnormal operating conditions. Model input parameters for local control measures and handling activities were refined to reflect pharmaceutical situations. RESULTS: The refined exposure model resulted in good correlations between the log-transformed model predictions and the actual measured data for the overall dataset (r(s) = 0.61, n = 381, p < 0.001) and at scenario level (r(s) = 0.69, n = 48, p < 0.001). The model overestimated scenarios with measured exposure levels < 0.1 mg m⁻³ (r(s) = 0.69, bias = 0.71, n = 46, p < 0.001), and underestimated scenarios with higher measured concentrations ( > 0.1 mg m⁻³) (r(s) = 0.59, bias = -4.9, n = 33, p < 0.001). Including information on the refined sub-parameters improved the correlations, suggesting the uncertainty in the model parameters was partly responsible for the bias. CONCLUSION: Further scientific data from the pharmaceutical industry on model input parameters, particularly on the efficacy of local control measures, may help improve the accuracy of the model predictions. The refined exposure model appears to be a useful exposure assessment screening tool for the pharmaceutical industry.

Exposure assessment of airborne contaminants in the indoor environment of Irish swine farms.

Agricultural workers have higher rates of long-term sick leave associated with respiratory disease than any other worker groups. There is currently no published data on the extent to which Irish agricultural workers are exposed to occupational respiratory hazards. This investigation focused on Irish swine farm workers in concentrated animal feeding operations and measured their occupational exposure to various respiratory hazards. Swine workers were found to be exposed to high concentrations of inhalable (0.25-7.6 mg/m(3)) and respirable (0.01-3.4 mg/m(3)) swine dust and airborne endotoxin (<166, 660 EU/m(3)). 8 hour Time Weighted Average ammonia and peak carbon dioxide exposures ranged from 0.01-3 ppm and 430- 4780 ppm, respectively. Results of this study suggest that Irish swine confinement workers have a potential risk of developing work-associated respiratory disease.