Radium dial watches,a potentially hazardous legacy?

This study re-examines the risk to health from radium (²²⁶Ra) dial watches. Ambient dose equivalent rates have been measured for fifteen pocket watches giving results of up to 30 μSv h^− 1 at a distance of 2 cm taken with a series 1000 mini-rad from the front face (arithmetic mean ambient dose equivalent for pocket watches being 13.2 μSv h^− 1). A pocket compass gave rise to a similar ambient dose equivalent rate, of 20 μSv h^− 1, to the pocket watches, with its cover open. Eighteen wristwatches have also been assessed, but their dose rates are generally much lower (the arithmetic mean being 3.0 μSv h^− 1), although the highest ambient dose equivalent rate noted was 20 μSv h^− 1. A phantom experiment using a TLD suggested an effective dose equivalent of 2.2 mSv/y from a 1 μCi (37 kBq) radium dial worn for 16 h/day throughout the year (dose rate 0.375 μSv h^− 1). For this condition we estimated maximum skin dose for our pocket watches as 16 mSv per year, with effective doses of 5.1 mSv and 1.169 mSv when worn in vest and trouser pockets respectively. This assumes exposure from the back of the watch which is generally around 60–67% of that from the front. The maximum skin dose from a wristwatch was 14 mSv, with 4.2 mSv effective dose in vest pocket. Radium (²²⁶Ra) decays to the radioactive gas radon (²²²Rn), and atmospheric radon concentration measurements taken around a pocket watch in a small sealed glass sphere recorded 18,728 Bq m^− 3. All watches were placed in a room with a RAD7 real-time radon detector. Radon concentration average was 259 ± 9 Bq m^− 3 over 16 h, compared to background average over 24 h of 1.02 Bq m^− 3. Over 6 weeks highs of the order of 2000 Bq m^− 3 were routinely recorded when the heating/ventilation system in the room was operating at reduced rates, peaking at over 3000 Bq m^− 3 on several occasions. Estimates of the activity of ²²⁶Ra in the watches ranged from 0.063 to 1.063 μCi (2.31 to 39.31 kBq) for pocket watches and from 0.013 to 0.875 μCi (0.46 to 32.38 kBq) for wrist watches. The risk from old watches containing radium appears to have been largely forgotten today. This paper indicates a health risk, particular to collectors, but with knowledge and appropriate precautions the potential risks can be reduced.     

Natural radionuclides in Austrian mineral water and their sequential measurement by fast methods

Ten samples of Austrian mineral water were investigated with regard to the natural radionuclides (228)Ra, (226)Ra, (210)Pb, (210)Po, (238)U and (234)U. The radium isotopes as well as (210)Pb were measured by liquid scintillation counting (LSC) after separation on a membrane loaded with element-selective particles (Empore Radium Disks) and (210)Po was determined by alpha-spectroscopy after spontaneous deposition onto a copper planchette. Uranium was determined by ICP-MS as well as by alpha-spectroscopy after ion separation and microprecipitation with NdF(3). From the measured activity concentrations the committed effective doses for adults and babies were calculated and compared to the total indicative dose of 0.1 mSv/a given in the EC Drinking Water Directive as a maximum dose. The dominant portion of the committed effective dose was due to the radium isotopes; the dose from (228)Ra in most samples clearly exceeded the dose from (226)Ra.     

A study of radium bioaccumulation in freshwater mussels, Velesunio angasi, in the Magela Creek catchment, Northern Territory, Australia

Freshwater mussels, Velesunio angasi, along Magela Creek in Australia’s Northern Territory were examined to study radionuclide activities in mussel flesh and to investigate whether the Ranger Uranium mine is contributing to the radium loads in mussels downstream of the mine. Radium loads in mussels of the same age were highest in Bowerbird Billabong, located 20 km upstream of the mine site. Variations in the ratio of [Ra]:[Ca] in filtered water at the sampling sites accounted for the variations found in mussel radium loads with natural increases in calcium (Ca) in surface waters in a downstream gradient along the Magela Creek catchment gradually reducing radium uptake in mussels. At Mudginberri Billabong, 12 km downstream of the mine, concentration factors for radium have not significantly changed over the past 25 years since the mine commenced operations and this, coupled with a gradual decrease of the ²²⁸Ra/²²⁶Ra activity ratios observed along the catchment, indicates that the ²²⁶Ra accumulated in mussels is of natural rather than mine origin. The ²²⁸Th/²²⁸Ra ratio has been used to model radium uptake and a radium biological half-life in mussels of approximately 13 years has been determined. The long biological half-life and the low Ca concentrations in the water account for the high radium concentration factor of 30,000-60,000 measured in mussels from the Magela Creek catchment.     

A study of radium uptake by the water-lily Nymphaea violacea (Lehm) from contaminated sediment

The rate and extent of radium-226 accumulation from sediment by the water-lily Nymphaea violacea (Lehm) were assessed. The plants were collected from Magela Creek, Northern Territory, Australia and grown in ²²⁶RaCl₂-labelled laboratory sediment over a period of 570 days. The nominal sediment activity of 5 Bq g⁻¹ dry weight was 100 times that of the naturally occurring concentration.In the roots and rhizomes, ²²⁶Ra accumulated on plant surfaces. This result was confirmed by autoradiographic studies which showed the presence of an iron-containing plaque on the surface of these tissues with which the radium was closely associated. Little radium reached the pith of the rhizomes and acropetal translocation was not detected. The average concentration ratio for growing rhizomes was 0·22. Assuming first order accumulation kinetics and likely incremental environmental concentrations, this Aboriginal dietary tissue could become dose-limiting within 50 years.The foliar accumulation of radium originating from the sediment was predominately due to contamination via the sediment-water-plant pathway. Differences in foliar radium concentrations in plants of different ages were due to differential biomass turnover rates. Plants with faster biomass turnover had higher average radium concentrations.     

Thyroid hormone disrupting activities associated with phthalate esters in water sources from Yangtze River Delta

Thyroid hormone disrupting compounds in water sources is a concern. Thyroid hormone (TH) agonist and antagonist activities of water sources from the Yangtze River, Huaihe River, Taihu Lake and ground water in the Yangtze River Delta region were evaluated by use of a TH reporter gene assay based on the green monkey kidney fibroblast (CV-1). While weak TH receptor (TR) agonist potency was observed in only one of 15 water sources, antagonist potency was present in most of the water sources. TR antagonist equivalents could be explained by the presence of dibutyl phthalate (DBP), with concentrations ranging from 2.8 × 10¹ to 1.6 × 10³ μg DBP /L (ATR-EQ₅₀s). None of the ground waters exhibited TH agonist potencies while all of the samples from Taihu Lake displayed notable TR antagonist potencies. To identify the responsible thyroid active compounds, instrumental analysis was conducted to measure a list of potential thyroid-disrupting chemicals, including organochlorine (OC) pesticides and phthalate esters. Combining the results of the instrumental analysis with those of the bioassay, DBP was determined to account for 17% to 144% of ATR-EQ₅₀s in water sources. Furthermore, ATR-EQ_20–80 ranges for TR antagonist activities indicated that samples from locations WX-1 and WX-2 posed the greatest health concern and the associated uncertainty may warrant further investigation.     

Soil radium, soil gas radon and indoor radon empirical relationships to assist in post-closure impact assessment related to near-surface radioactive waste disposal

Least squares (LS), Theil’s (TS) and weighted total least squares (WTLS) regression analysis methods are used to develop empirical relationships between radium in the ground, radon in soil and radon in dwellings to assist in the post-closure assessment of indoor radon related to near-surface radioactive waste disposal at the Low Level Waste Repository in England. The data sets used are (i) estimated ²²⁶Ra in the <2 mm fraction of topsoils (eRa226) derived from equivalent uranium (eU) from airborne gamma spectrometry data, (ii) eRa226 derived from measurements of uranium in soil geochemical samples, (iii) soil gas radon and (iv) indoor radon data. For models comparing indoor radon and (i) eRa226 derived from airborne eU data and (ii) soil gas radon data, some of the geological groupings have significant slopes. For these groupings there is reasonable agreement in slope and intercept between the three regression analysis methods (LS, TS and WTLS). Relationships between radon in dwellings and radium in the ground or radon in soil differ depending on the characteristics of the underlying geological units, with more permeable units having steeper slopes and higher indoor radon concentrations for a given radium or soil gas radon concentration in the ground. The regression models comparing indoor radon with soil gas radon have intercepts close to 5 Bq m⁻³ whilst the intercepts for those comparing indoor radon with eRa226 from airborne eU vary from about 20 Bq m⁻³ for a moderately permeable geological unit to about 40 Bq m⁻³ for highly permeable limestone, implying unrealistically high contributions to indoor radon from sources other than the ground. An intercept value of 5 Bq m⁻³ is assumed as an appropriate mean value for the UK for sources of indoor radon other than radon from the ground, based on examination of UK data. Comparison with published data used to derive an average indoor radon: soil ²²⁶Ra ratio shows that whereas the published data are generally clustered with no obvious correlation, the data from this study have substantially different relationships depending largely on the permeability of the underlying geology. Models for the relatively impermeable geological units plot parallel to the average indoor radon: soil ²²⁶Ra model but with lower indoor radon: soil ²²⁶Ra ratios, whilst the models for the permeable geological units plot parallel to the average indoor radon: soil ²²⁶Ra model but with higher than average indoor radon: soil ²²⁶Ra ratios.     

Source of radium in a well-water-augmented Florida lake

A study of the lake waters of Saddleback Lake, Florida was undertaken with the goal of determining the source of elevated radium activities in the lake. Four radium isotopes, (226)Ra, (228)Ra, (223)Ra and (224)Ra, were measured and activities of all the four radium isotopes were substantially greater in the well water used to augment the lake as compared to the lake waters. In the surface water, radium activities were highest close to the well used for augmentation in the initial sampling. Activities initially decreased with time after augmentation from the well ceased. The (223)Ra/(226)Ra activity ratio decreased during the first month of sampling and closely followed an exponential decay curve based on the (223)Ra decay constant. Trends in the activities and the (223)Ra/(226)Ra activity ratios support the conclusion that the well used to augment the lake was the dominant source of (223)Ra and (226)Ra to Saddleback Lake during this study. The (224)Ra/(226)Ra activity ratio did not follow the expected trend of exponential decay based on the (224)Ra decay constant. While the augmentation well supplied some (224)Ra, these results suggest that there must be an additional source of (224)Ra to the lake. The most likely additional source of (224)Ra appears to be the ingrowth of (224)Ra on the sediment within the lake from (228)Ra (via (228)Th).     

Radionuclide concentrations in soil and lifetime cancer risk due to gamma radioactivity in Kirklareli,Turkey

The objective of this study is to evaluate and map soil radionuclides' activity concentrations and environmental outdoor gamma dose rates (terrestrial and cosmic) in Kirklareli, Turkey. The excess lifetime cancer risks are also calculated. Outdoor gamma dose rates were determined in 230 sampling stations and soil samples were taken from 177 locations. The coordinates of the readings were determined by the Global Positioning System (GPS). The outdoor gamma dose rates were determined by Eberline smart portable device (ESP-2) and measurements were taken in air for two minutes at 1 m from the ground. The average outdoor gamma dose rate was 118 ± 34 nGy h^?1. Annual effective gamma dose of Kirklareli was 144 μSv and the excess lifetime cancer risk of 5.0 × 10^?4. Soil samples were analyzed by gamma spectroscopy. The average ²²⁶Ra, ²³⁸U, ²³²Th, ¹³⁷Cs, and ⁴⁰K activities were 37 ± 18 Bq kg^?1, 28 ± 13 Bq kg^?1, 40 ± 18 Bq kg^?1, 8 ± 5 Bq kg^?1 and 667 ± 281 Bq kg^?1, respectively. The average soil radionuclides' concentrations of Kirklareli were within the worldwide range although some extreme values had been determined. Annual effective gamma doses and the excess lifetime risks of cancer were higher than the world's average.     

Risks associated with the transfer of toxic organo-metallic mercury from soils into the terrestrial feed chain

Although the transfer of organo-metallic mercury (OrgHg) in aquatic food webs has long been studied, it has only been recently recognized that there is also accumulation in terrestrial systems. There is still however little information about the exposure of grazing animals to OrgHg from soils and feed as well as on risks of exposure to animal and humans.In this study we collected 78 soil samples and 40 plant samples (Lolium perenne and Brassica juncea) from agricultural fields near a contaminated industrial area and evaluated the soil-to-plant transfer of Hg as well as subsequent trophic transfer. Inorganic Hg (IHg) concentrations ranged from 0.080 to 210 mg kg^− 1 d.w. in soils, from 0.010 to 84 mg kg^− 1 d.w. in roots and from 0.020 to 6.9 mg kg^− 1 d.w. in shoots. OrgHg concentrations in soils varied between 0.20 and 130 μg kg^− 1 d.w. representing on average 0.13% of the total Hg (THg). In root and shoot samples OrgHg comprised on average 0.58% (roots) and 0.66% (shoots) of THg. Average bioaccumulation factors (BAFs) for OrgHg in relation to soil concentrations were 3.3 (for roots) and 1.5 (for shoots).The daily intake (DI) of THg in 33 sampling sites exceeded the acceptable daily intake (ADI) of THg of both cows (ADI = 1.4 mg d^− 1) and sheep (ADI = 0.28 mg d^− 1), in view of food safety associated with THg in animal kidneys. Estimated DI of OrgHg for grazing animals were up to 220 μg d^− 1 (for cows) and up to 33 μg d^− 1 (for sheep).This study suggested that solely monitoring the levels of THg in soils and feed may not allow to adequately taking into account accumulation of OrgHg in feed crops and properly address risks associated with OrgHg exposure for animals and humans. Hence, the inclusion of limits for OrgHg in feed quality and food safety legislation is advised.     

Determination of heavy metals in indoor dust from Istanbul,Turkey: Estimation of the health risk

Levels of eight potentially toxic heavy metals in indoor dust from homes and offices in Istanbul were investigated. The concentrations of heavy metals in indoor dust from homes + office ranged from 62 to 1800 μg g^− 1 for Cu, 3–200 μg g^− 1 for Pb, 0.4–20 μg g^− 1 for Cd, 210–2800 μg g^− 1 for Zn, 2.8–460 μg g^− 1 for Cr, 8–1300 μg g^− 1 for Mn, 2.4–25 μg g^− 1 for Co, 120–2600 μg g^− 1 for Ni. Results of the study were comparable to other studies conducted on indoor dust and street dust from a variety of cities globally. Considering only ingestion + inhalation, the carcinogenic risk level of Cr for adults and children (3.7 × 10^− 5 and 2.7 × 10^− 5) in Istanbul was in the range of EPA's safe limits (1 × 10^− 6 and 1 × 10^− 4), indicating that cancer risk of Cr due to exposure to indoor dust in Istanbul can be acceptable. According to calculated Hazard Quotient (HQ), for non-cancer effects, the ingestion of indoor dust appears to be the major route of exposure to the indoor dust that results in a higher risk for heavy metals, followed by dermal contact and inhalation pathways. However, compared to ingestion and dermal contact exposure, exposure through inhalation is almost negligible. Hazard Index (HI) values for all studied elements were lower than safe limit of 1 and this result suggested that none of the population groups would likely to experience potential health risk due to exposure to heavy metals from indoor dust in the study area.     

90Sr, 210Po and 210Pb in lichen and reindeer in Norway

Concentrations of ⁹⁰Sr, ²¹⁰Po and ²¹⁰Pb in lichen and reindeer were studied in central (Østre Namdal) and southern Norway (Vågå) during 2000–2003. The study focussed on potential differences in concentrations of these nuclides in reindeer of different ages. Concentrations of ⁹⁰Sr in bones of ∼10 year old adult females were about 40% higher than those in calves' antlers (⁹⁰Sr concentrations in antlers and bones of calves are similar), while the available data from Vågå suggest that ⁹⁰Sr concentrations in reindeer calves decreased with an effective ecological half-time of 9.03 ± 0.06 years during 1988–2002. Furthermore, ⁹⁰Sr concentrations were 50–80% higher in bone of reindeer of a similar age from Vågå compared to those from Østre Namdal. Concentrations of ²¹⁰Po and ²¹⁰Pb in muscle and liver tissues were comparable to those reported for reindeer in other Nordic areas, with no significant difference in ²¹⁰Po and ²¹⁰Pb concentrations between adults and calves or between reindeer from the two different study areas.     

Measuring the radium quartet (Ra, Ra, Ra, Ra) in seawater samples using gamma spectrometry

Radium isotopes are widely used in marine studies (eg. to trace water masses, to quantify mixing processes or to study submarine groundwater discharge). While ²²⁸Ra and ²²⁶Ra are usually measured using gamma spectrometry, short-lived Ra isotopes (²²⁴Ra and ²²³Ra) are usually measured using a Radium Delayed Coincidence Counter (RaDeCC). Here we show that the four radium isotopes can be analyzed using gamma spectrometry. We report ²²⁶Ra, ²²⁸Ra, ²²⁴Ra, ²²³Ra activities measured using low-background gamma spectrometry in standard samples, in water samples collected in the vicinity of our laboratory (La Palme and Vaccarès lagoons, France) but also in seawater samples collected in the plume of the Amazon river, off French Guyana (AMANDES project). The ²²³Ra and ²²⁴Ra activities determined in these samples using gamma spectrometry were compared to the activities determined using RaDeCC. Activities determined using the two techniques are in good agreement. Uncertainties associated with the ²²⁴Ra activities are similar for the two techniques. RaDeCC is more sensitive for the detection of low ²²³Ra activities. Gamma spectrometry thus constitutes an alternate method for the determination of short-lived Ra isotopes.     

The ‘take home’ burden of workplace sensitizers: Flour contamination in bakers' families

BackgroundExposure to flour/flour constituents is a leading cause of occupational asthma. Paternal occupational exposure to flour has been associated with increased likelihood of childhood asthma, raising the possibility of para-occupational exposure whereby family members are exposed to sensitizers ‘taken home’ on contaminated skin/clothing.ObjectiveTo establish whether workplace contamination of skin/clothing with wheat flour allergen (WFA) and fungal α-amylase (FAA) is associated with increased levels of these allergens in bakers' homes.MethodsBakeries in north-east Scotland were invited to participate. Control subjects were recruited from University of Aberdeen staff and students. Exposure assessment was carried out in bakeries, bakers' cars and the homes of bakers and controls using surface wipe and vacuum sampling; samples were analyzed for total protein, FAA and WFA.Results164 wipe samples and 49 vacuum samples were collected from 38 bakers (from 5 bakeries) and 10 controls.Compared to non-bakers, bakers had higher median levels of WFA and FAA in house vacuum samples; the difference was statistically significant for WFA/total protein (515.8 × 10^− 6 vs. 163.7 × 10^− 6, p = 0.031), FAA/total protein ratios (1.45 × 10^− 6 vs. 0.04 × 10^− 6, p < 0.001) and FAA loading (median 1.2 pg/cm² vs. 0.1 pg/cm², p < 0.001) with workplace exposure–home contamination relationships between bakers with higher and lower workplace contamination.We found positive correlations between WFA contamination of the bakers' foreheads and cars (r_s0.57, p = 0.028), foreheads and houses (r_s0.46, p = 0.025), shoes and houses (r_s0.45, p = 0.029); and between FAA contamination of shoes and houses (r_s0.46, p = 0.023), and cars and houses (r_s0.70, p = 0.008). There was no evidence of bakers using work-sourced flour for domestic baking.ConclusionsThis work demonstrates pathways for ‘take home’ exposure of occupationally sourced flour. Taken with our previous work, showing that bakers' children are more likely to have asthma, this supports the need for further investigation to establish whether ‘take home’ of occupationally sourced flour is widespread with health consequences.     

Organic micropollutants in coastal waters from NW Mediterranean Sea: Sources distribution and potential risk

This study provides a first estimation on the sources, distribution and risk of organic micropollutants (OMPs) in coastal waters from NW Mediterranean Sea. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, polybrominated diphenyl ethers, phthalates and alkylphenols were analyzed by solid phase extraction and gas chromatography coupled to tandem mass spectrometry (SPE–GC–EI-MS/MS). River waters and wastewater treatment plant effluents discharging to the sea were identified as the main sources of OMPs to coastal waters, with an estimated input amount of around of 25,800 g d^− 1. The concentration of ΣOMPs in coastal areas ranged from 17.4 to 8442 ng L^− 1, and was the highest in port waters, followed by coastal and river mouth seawaters. A summarized overview of the patterns and sources of OMP contamination on the investigated coastal sea waters of NW Mediterranean Sea, as well as of their geographical distribution was obtained by Principal Component Analysis of the complete data set after its adequate pretreatment. Alkylphenols, bisphenol A and phthalates were the main contributors to ΣOMPs and produced an estimated significant pollution risk for fish, algae and the sensitive mysid shrimp organisms in seawater samples. The combination of GC-MS/MS, chemometrics and risk analysis is proven to be useful for a better control and management of OMP discharges.     

Monocyclic and bicyclic monoterpenes in air of German daycare centers and human biomonitoring in visiting children,the LUPE 3 study

To investigate the assumed association between indoor air pollution with monoterpenes (MTps) and the internal MTp exposure of occupants, a comparative study was performed in daycare centers in two federal states of Germany. Three well-known monoterpenoid air pollutants, viz. α-pinene (αPN), Δ³-carene (CRN), and R-limonene (LMN), were measured in indoor air in 45 daycare centers. Additionally, urine samples of 222 children visiting these facilities were collected in the evening after a full-day stay. Altogether 11 MTp metabolites were analyzed in the urine samples using a novel highly sensitive and selective gas chromatographic–tandem-mass spectrometric procedure. The medians (95th percentiles) of the MTp levels in indoor air were 9.1 μg m^− 3 (94 μg m^− 3) for LMN, 2.6 μg m^− 3 (13 μg m^− 3) for αPN, and < 1.0 μg m^− 3 (3.2 μg m^− 3) for CRN. None of the day care centers exceeded the German health precaution or hazard guide value. In spite of the low MTp air exposure, the urine analyses revealed an exposure to the three monoterpenes in almost all children. The median levels of MTp metabolites in urine were 0.11 mg L^− 1 for LMN-8,9-OH, 0.10 mg L^− 1 for LMN-1,2-OH, 49 μg L^− 1 for PA, 2.9 μg L^− 1 for POH, 5.2 μg L^− 1 for tCAR, and 4.1 μg L^− 1 for cCAR (LMN metabolites), 7.2 μg L^− 1 for MYR, 19 μg L^− 1 for tVER, and 19 μg L^− 1 for cVER (αPN metabolites), as well as 8.2 μg L^− 1 for CRN-10-COOH (CRN metabolite). Statistically significant and strong correlations among the urinary metabolites of each MTp were found. Moreover, statistical associations between LMN metabolites and the LMN indoor air levels were revealed. However, the weakness of the associations indicates a considerable impact of other MTp sources, e.g. diet and consumer products, on the internal exposure.     

Hydroxylated and methoxylated polybrominated diphenyl ethers in blood plasma of humans in Hong Kong

Hydroxylated (OH-) and methoxylated (MeO-) polybrominated diphenyl ethers (PBDE) are suspected endocrine disruptors. Little is known about the accumulation or sources of these chemicals in tissues of humans, particularly those residing in Hong Kong, which is one of the most densely populated cities in the world. Seven MeO-BDEs, fifteen OH-BDEs and three bromophenols (BRPs) were analyzed in blood plasma of 116 humans that had been collected by the Hong Kong Red Cross. Total concentrations of MeO-BDEs, OH-BDEs and BRPs ranged from 3.8 × 10² to 52 × 10³ pg g^− 1 lipid (median 4.5 × 10³ pg g^− 1), 5.3 to 4.9 × 10² pg g^− 1 lipid (81 pg g^− 1) and ND to 1.1 × 10² pg g^− 1 lipid (3.7 pg g^− 1), respectively. 3-MeO-BDE-47, 6-OH-BDE-47 and 2, 4, 5-TBP were the predominant MeO-BDEs, OH-BDEs and BRPs, respectively. These results are consistent with accumulation of MeO-BDEs, OH-BDEs and BRPs in human plasma being primarily from natural products and inter-conversion of natural products. Coefficients of determination for some pairs of congeners such as 3-OH-BDE-100 and 6-OH-BDE-47, 6-OH-BDE-85 and 5′-OH-BDE-99, and 2, 4-DBP and 6-OH-BDE-85, were near 1.0, which is consistent with them having common sources. Patterns of relative concentrations of the target analytes were similar in the diet, particularly fish, as in blood plasma of humans, which suggests that the diet and particularly seafood might be a source of these compounds and PBDEs. Furthermore, biotransformation of natural chemicals such as OH-BDEs to BRPs might be the primary route of their elimination from humans.     

The contributions to long-term health-relevant particulate matter at the UK EMEP supersites between 2010 and 2013: Quantifying the mitigation challenge

Human health burdens associated with long-term exposure to particulate matter (PM) are substantial. The metrics currently recommended by the World Health Organization for quantification of long-term health-relevant PM are the annual average PM₁₀ and PM_2.5 mass concentrations, with no low concentration threshold. However, within an annual average, there is substantial variation in the composition of PM associated with different sources. To inform effective mitigation strategies, therefore, it is necessary to quantify the conditions that contribute to annual average PM₁₀ and PM_2.5 (rather than just short-term episodic concentrations). PM₁₀, PM_2.5, and speciated water-soluble inorganic, carbonaceous, heavy metal and polycyclic aromatic hydrocarbon components are concurrently measured at the two UK European Monitoring and Evaluation Programme (EMEP) ‘supersites’ at Harwell (SE England) and Auchencorth Moss (SE Scotland). In this work, statistical analyses of these measurements are integrated with air-mass back trajectory data to characterise the ‘chemical climate’ associated with the long-term health-relevant PM metrics at these sites. Specifically, the contributions from different PM concentrations, months, components and geographic regions are detailed. The analyses at these sites provide policy-relevant conclusions on mitigation of (i) long-term health-relevant PM in the spatial domain for which these sites are representative, and (ii) the contribution of regional background PM to long-term health-relevant PM.At Harwell the mean (± 1 sd) 2010–2013 annual average concentrations were PM₁₀ = 16.4 ± 1.4 μg m^− 3 and PM_2.5 = 11.9 ± 1.1 μg m^− 3 and at Auchencorth PM₁₀ = 7.4 ± 0.4 μg m^− 3 and PM_2.5 = 4.1 ± 0.2 μg m^− 3. The chemical climate state at each site showed that frequent, moderate hourly PM₁₀ and PM_2.5 concentrations (defined as approximately 5–15 μg m^− 3 for PM₁₀ and PM_2.5 at Harwell and 5–10 μg m^− 3 for PM₁₀ at Auchencorth) determined the magnitude of annual average PM₁₀ and PM_2.5 to a greater extent than the relatively infrequent high, episodic PM₁₀ and PM_2.5 concentrations. These moderate PM₁₀ and PM_2.5 concentrations were derived across the range of chemical components, seasons and air-mass pathways, in contrast to the highest PM concentrations which tended to associate with specific conditions. For example, the largest contribution to moderate PM₁₀ and PM_2.5 concentrations – the secondary inorganic aerosol components, specifically NO₃⁻ – were accumulated during the arrival of trajectories traversing the spectrum of marine, UK, and continental Europe areas. Mitigation of the long-term health-relevant PM impact in the regions characterised by these two sites requires multilateral action, across species (and hence source sectors), both nationally and internationally; there is no dominant determinant of the long-term PM metrics to target.     

Spatiotemporal analysis and human exposure assessment on polycyclic aromatic hydrocarbons in indoor air,settled house dust,and diet: A review

This review summarizes the published literature on the presence of polycyclic aromatic hydrocarbons (PAH) in indoor air, settled house dust, and food, and highlights geographical and temporal trends in indoor PAH contamination. In both indoor air and dust, ΣPAH concentrations in North America have decreased over the past 30 years with a halving time of 6.7 ± 1.9 years in indoor air and 5.0 ± 2.3 years in indoor dust. In contrast, indoor PAH concentrations in Asia have remained steady. Concentrations of ΣPAH in indoor air are significantly (p < 0.01) higher in Asia than North America. In studies recording both vapor and particulate phases, the global average concentration in indoor air of ΣPAH excluding naphthalene is between 7 and 14,300 ng/m³. Over a similar period, the average ΣPAH concentration in house dust ranges between 127 to 115,817 ng/g. Indoor/outdoor ratios of atmospheric concentrations of ΣPAH have declined globally with a half-life of 6.3 ± 2.3 years. While indoor/outdoor ratios for benzo[a]pyrene toxicity equivalents (BaP_eq) declined in North America with a half-life of 12.2 ± 3.2 years, no significant decline was observed when data from all regions were considered. Comparison of the global database, revealed that I/O ratios for ΣPAH (average = 4.3 ± 1.3), exceeded significantly those of BaP_eq (average = 1.7 ± 0.4) in the same samples. The significant decline in global I/O ratios suggests that indoor sources of PAH have been controlled more effectively than outdoor sources. Moreover, the significantly higher I/O ratios for ΣPAH compared to BaP_eq, imply that indoor sources of PAH emit proportionally more of the less carcinogenic PAH than outdoor sources. Dietary exposure to PAH ranges from 137 to 55,000 ng/day. Definitive spatiotemporal trends in dietary exposure were precluded due to relatively small number of relevant studies. However, although reported in only one study, PAH concentrations in Chinese diets exceeded those in diet from other parts of the world, a pattern consistent with the spatial trends observed for concentrations of PAH in indoor air. Evaluation of human exposure to ΣPAH via inhalation, dust and diet ingestion, suggests that while intake via diet and inhalation exceeds that via dust ingestion; all three pathways contribute and merit continued assessment.     

Within-room and within-building temporal and spatial variations in concentrations of polybrominated diphenyl ethers (PBDEs) in indoor dust

Within-house and within-room spatial temporal variability in PBDE contamination of indoor dust may influence substantially the reliability of human exposure assessments based on single point samples, but have hitherto been little studied. This paper reports concentrations of PBDEs 17, 28, 47, 49, 66, 85, 99, 100, 153, and 154 in indoor dust samples (n = 112) from two houses in Birmingham, UK. To evaluate within-house spatial variability, four separate rooms were sampled in house 1 and two separate rooms sampled in house 2. Up to four different 1 m² areas in the same room were sampled to evaluate within-room spatial variability, and for all studied areas, samples were taken for eight consecutive months to evaluate temporal and seasonal variability. Concentrations of ΣPBDEs in individual samples from house 1 varied between 21 and 280 ng g^− 1; while the range of concentrations in house 2 was 20–1000 ng g^− 1. This indicates that where and when a sample is taken in a house can influence substantially the contamination detected. In one room, concentrations of PBDEs in an area located close to putative PBDE sources exceeded substantially those in an area 2 m away, with marked differences also observed between two areas in another room. Substantial within-room spatial differences in PBDE concentrations were not discernible in the other rooms studied. Concentrations of PBDEs in the majority of rooms within the same houses were not markedly different between rooms. Nevertheless, large differences were observed between PBDE concentrations detected in two rooms in the same house in both houses studied. In one instance, this is hypothesised to be attributable to the presence of a carpet in one room and bare wooden floor in another, but firm conclusions cannot be drawn. Within-room temporal (month-to-month) variability was substantial (relative standard deviations for ΣPBDEs = 15–200%). In some rooms, the introduction and removal of putative sources like a TV and a bed, appeared to exert a discernible influence on PBDE concentrations. PBDE concentrations in spring and summer were not markedly different from those observed in autumn and winter. Possible dilution of PBDE concentrations in dust at higher dust loadings (g dust per m² floor surface) was investigated in a small number of rooms, but no firm evidence of such dilution was evident.     

Can car air filters be useful as a sampling medium for air pollution monitoring purposes?

Urban air quality and real human exposure to chemical environmental stressors is an issue of high scientific and political interest. In an effort to find innovative and inexpensive means for air quality monitoring, the ability of car engine air filters (CAFs) to act as efficient samplers collecting street level air, to which people are exposed to, was tested. In particular, in the case of taxis, air filters are replaced after regular distances, the itineraries are almost exclusively urban, cruising mode is similar and, thus, knowledge of the air flow can provide with an integrated city air sample. The present pilot study focused on polycyclic aromatic hydrocarbons (PAHs), the most important category of organic pollutants associated with traffic emissions. Concentrations of ΣPAHs in CAFs ranged between 650 and 2900 μg CAF^− 1, with benzo[b]fluoranthene, benzo[k]fluoranthene and indeno[123-cd]pyrene being the most abundant PAHs. Benzo[a]pyrene (BaP) ranged between 110 and 250 μg CAF^− 1, accounting regularly for 5–15% of the total carcinogenic PAHs. The CAF PAH loads were used to derive road-level atmospheric PAH concentrations from a standard formula relating to the CAF air flow. Important parameters/assumptions for these estimates are the cruising speed and the exposure duration of each CAF. Based on information obtained from the garage experts, an average ‘sampled air volume’ of 48,750 m³ per CAF was estimated, with uncertainty in this calculation estimated to be about a factor of 4 between the two extreme scenarios. Based on this air volume, ΣPAHs ranged between 13 and 56 ng m^− 3 and BaP between 2.1 and 5.0 ng m^− 3, suggesting that in-traffic BaP concentrations can be many times higher than the limit values set by the UK (0.25 ng m^− 3) and the European Union (1.0 ng m^− 3), or from active sampling stations normally cited on building roof tops or far from city centres.Notwithstanding the limitations of this approach, the very low cost, the continuous availability of very high amounts of “sample”, and the “retroactivity” render it very useful and complementary to existing passive sampling techniques. This approach yields estimated air concentrations that reflect the pollutant concentrations to which taxi drivers, pedestrians, cyclists and road-related professionals are exposed.