Priority and emerging flame retardants in rivers: Occurrence in water and sediment,Daphnia magna toxicity and risk assessment

The occurrence, partitioning and risk of eight polybrominated diphenyl ethers (PBDEs), nine new brominated (NBFRs) and ten organophosphorus flame retardants (OPFRs) were evaluated in three Spanish rivers suffering different anthropogenic pressures (Nalón, Arga and Besòs). OPFRs were ubiquitous contaminants in water (ΣOPFRs ranging from 0.0076 to 7.2 μg L^− 1) and sediments (ΣOPFRs ranging 3.8 to 824 μg kg^− 1). Brominated flame retardants were not detected in waters, whereas ΣPBDEs ranged from 88 to 812 μg kg^− 1 and decabromodiphenyl ethane (DBDPE) reached 435 μg kg^− 1 in sediments from the River Besòs, the most impacted river. The occurrence of flame retardants in river water and sediment was clearly associated with human activities, since the highest levels occurred near urban and industrial zones and after wastewater treatment plants discharge. Daphnia magna toxicity was carried out for OPFRs, the most ubiquitous flame retardants, considering individual compounds and mixtures. Toxicity of nine tested OPFRs differed largely among compounds, with EC₅₀ values ranging over three magnitude orders (0.31–381 mg L^− 1). Results evidenced that these compounds act by non-polar narcosis, since their toxicity was proportional to their lipophilicity (K_ow). Furthermore, their joint toxicity was additive, which means that single and joint toxicity can be predicted knowing their concentration levels in water using quantitative structure activity relationships (QSARs) and predictive mixture models. Based on these results, a risk assessment considering joint effect was performed calculating and summing risk quotients (RQs) for the water and sediment samples. No significant risk to D. magna (ΣRQs < 1) was observed for any of the monitored rivers.     

Anthropogenic radionuclides in sediment in the Japan Sea: distribution and transport processes of particulate radionuclides

Distributions of anthropogenic radionuclides (⁹⁰Sr, ¹³⁷Cs and ^239+240Pu) in seabed sediment in the Japan Sea were collected during the period 1998–2002. Concentration of ⁹⁰Sr, ¹³⁷Cs and ^239+240Pu in seabed sediment was 0.07–1.6 Bq kg⁻¹, 0.4–9.1 Bq kg⁻¹ and 0.002–1.9 Bq kg⁻¹, respectively. In the northern basin of the sea (Japan Basin), ^239+240Pu/¹³⁷Cs ratios in seabed sediment were higher and their variation was smaller compared to that in the southeastern regions of the sea. The higher ^239+240Pu/¹³⁷Cs ratios throughout the Japan Basin were considered to reflect production of Pu-enriched particles in the surface layer and substantial sinking of particulate materials in this region. In the southern regions of the Japan Sea (<38°N), both inventories and ^239+240Pu/¹³⁷Cs ratios in sediment were larger than those in the other regions. In the southern Japan Sea, observations suggested that supply of particulate radionuclides by the Tsushima Warm Current mainly enhanced accumulation of the radionuclides in this region.     

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.     

Rice consumption contributes to low level methylmercury exposure in southern China

Fish consumption is considered as the primary pathway of human methylmercury (MeHg) exposure. However, recent studies highlighted that, rice, rather than fish, is the main route of human MeHg exposure in Guizhou, inland China. China is considered as the largest anthropogenic source of mercury (Hg) emission in the world, which has led to serious environmental Hg pollution. But there are no comprehensive studies regarding this environmental health problem to evaluate human Hg exposure and associated health effects. This study aimed to estimate daily MeHg intake and health risk in 7 provinces in southern China, and to assess the relative contribution from rice and fish consumption. The average levels of total mercury (THg) and MeHg in rice samples were generally low at 10.1 ng·g^− 1 and 2.47 ng·g^− 1, respectively. But a total of 36 rice samples (12.7%) had THg concentration exceeding the national limit (20 ng·g^− 1). Generally, rural population had significantly higher Probable Daily Intakes (PDIs) of MeHg than urban population from rice consumption and its relative contribution to MeHg exposure increased significantly from coastal to inland area. The averages of PDIs of MeHg were 0.020 μg·kg^− 1·d^− 1 and 0.028 μg·kg^− 1·d^− 1 for urban and rural population in southern China, respectively. Despite the serious environmental Hg pollutions in China, the general population in southern China had low risk of MeHg exposure. But rice is an important route of human MeHg exposure in southern China, especially for the rural population in inland area. The findings indicate that rice consumption should be considered when evaluating MeHg exposure in rice eating population in southern China.     

Phthalates in house dust

The main objective of this study was to generate a fast analytical method to determine the five phthalates benzylbutylphthalate (BBP), dibutylphthalate (DBP), di-(2-ethylhexyl)-phthalate (DEHP), di-isodecylphthalate (DIDP), and di-isononylphthalate (DINP) in house dust. To achieve this liquid chromatography electrospray tandem mass spectrometry (LC–ESI–MS/MS) was used for measurement. The risk of lab- and cross-contamination was nearly eliminated completely as a very short and fast sample preparation including a sieving step and an ultrasonic extraction for the analytes from the dust samples was used. Quantification through internal standard calibration resulted in low limits of determination (DEHP 4 mg kg^? 1 to DBP 14 mg kg^? 1). A potential interaction between the analytes DIDP and DINP during chromatographic measurement could be excluded while performing a two level factorial design. Furthermore it was examined to what extend carpet and plastic materials respectively have influence on the total amount of phthalates in dust. It could be shown that apartments in which a minimum of both of these sources appeared revealed the lowest total amount of sum of phthalates in dust (median 362 mg kg^? 1).     

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.     

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.     

Personal exposure to HBCDs and its degradation products via ingestion of indoor dust

Personal exposures via ingestion of indoor dust to α-, β-, and γ-hexabromocyclododecanes (HBCDs) and the degradation products (pentabromocyclododecenes (PBCDs) and tetrabromocyclododecadienes (TBCDs)) were estimated for 21 UK adults. Under an average dust ingestion scenario, personal exposures ranged from 4.5 to 1851 ng ΣHBCDs day^? 1; while the range under a high dust ingestion scenario was 11 to 4630 ng ΣHBCDs day^? 1. On average, personal exposure to ΣHBCDs via dust ingestion in this study was 35% α-, 11% β-, and 54% γ-HBCD. However, while exposure to β-HBCD (4–18% of ΣHBCDs) was relatively consistent with the proportion of this diastereomer in the HBCD commercial formulation; exposures to α- and γ-isomers (11–58% and 29–82% of ΣHBCDs respectively) showed substantial variation from the commercial formulation pattern. Personal exposures to ΣTBCDs (median = 0.2 ng day^? 1 under an average dust ingestion scenario) and ΣPBCDs (1.4 ng day^? 1) were significantly lower (p < 0.05) than for ΣHBCDs (48 ng day^? 1). Despite this, the exposure of one participant to ΣPBCDs exceeded the exposure to ΣHBCDs received by 85% of the other participants. On average, house dust provided the major contribution to personal exposure via dust ingestion to all target compounds due to the large time fraction spent in houses. In contrast, although participants spent less time in cars than in offices, car dust makes a higher average contribution (17%) to ΣHBCDs exposure than office dust (13%).     

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.     

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.     

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.     

Mechanistic polychlorinated biphenyl exposure modeling of mothers in the Canadian Arctic: the challenge of reliably establishing dietary composition

BackgroundTraditional food (TF) consumption represents the main route of persistent organic pollutant (POP) exposure for indigenous Arctic Canadians. Ongoing dietary transitions away from TFs and toward imported foods (IFs) may contribute to decreasing POP exposures observed in these groups.MethodsTo explore this issue, we combined the global fate and transport model GloboPOP and the human food chain bioaccumulation model ACC-Human Arctic to simulate polychlorinated biphenyl (PCB) exposure in two indigenous Arctic Canadian communities from the Inuvik region, Northwest Territories and Baffin region, Nunavut. Using dietary survey information from initial (1996–98) and follow-up (2005–07) biomonitoring campaigns in Inuvik and Baffin, we simulated PCB exposures (PCB-118, -138, -153, and -180) for each individual study participant and also whole study populations.ResultsTF intake rates, particularly of marine mammals (MMs), were the most important predictors of modeled PCB exposure, while TF consumption did not associate consistently with measured PCB exposures. Further, reported mean TF intake increased from baseline to follow-up in both Inuvik (from 8 to 183 g d^− 1) and Baffin (from 60 to 134 g d^− 1), opposing both the expected dietary transition direction and the observed decrease in human PCB exposures in these communities (ΣPCB Inuvik: from 43 to 29 ng g lipid^− 1, ΣPCB Baffin: from 213 to 82 ng g lipid^− 1). However dietary questionnaire data are frequently subject to numerous biases (e.g., recall, recency, confirmation), and thus casts doubt on the usefulness of these data.ConclusionsUltimately, our model's capability to reproduce historic PCB exposure data in these two groups was highly sensitive to TF intake, further underscoring the importance of accurate TF consumption reporting, and clarification of the role of dietary transitions in future POP biomonitoring of indigenous Arctic populations.     

Recreational swimmers' exposure to Vibrio vulnificus and Vibrio parahaemolyticus in the Chesapeake Bay,Maryland, USA

Vibrio vulnificus and Vibrio parahaemolyticus are ubiquitous in the marine–estuarine environment, but the magnitude of human non-ingestion exposure to these waterborne pathogens is largely unknown. We evaluated the magnitude of dermal exposure to V. vulnificus and V. parahaemolyticus among swimmers recreating in Vibrio-populated waters by conducting swim studies at four swimming locations in the Chesapeake Bay in 2009 and 2011. Volunteers (n = 31) swam for set time periods, and surface water (n = 25) and handwash (n = 250) samples were collected. Samples were analyzed for Vibrio concentrations using quantitative PCR. Linear and logistic regressions were used to evaluate factors associated with recreational exposures. Mean surface water V. vulnificus and V. parahaemolyticus concentrations were 1128 CFU mL^− 1 (95% confidence interval (CI): 665.6, 1591.4) and 18 CFU mL^− 1 (95% CI: 9.8, 26.1), respectively, across all sampling locations. Mean Vibrio concentrations in handwash samples (V. vulnificus, 180 CFU cm^− 2 (95% CI: 136.6, 222.5); V. parahaemolyticus, 3 CFU cm^− 2 (95% CI: 2.4, 3.7)) were significantly associated with Vibrio concentrations in surface water (V. vulnificus, p < 0.01; V. parahaemolyticus, p < 0.01), but not with salinity or temperature (V. vulnificus, p = 0.52, p = 0.17; V. parahaemolyticus, p = 0.82, p = 0.06). Handwashing reduced V. vulnificus and V. parahaemolyticus on subjects' hands by approximately one log (93.9%, 89.4%, respectively). It can be concluded that when Chesapeake Bay surface waters are characterized by elevated concentrations of Vibrio, swimmers and individuals working in those waters could experience significant dermal exposures to V. vulnificus and V. parahaemolyticus, increasing their risk of infection.     

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.     

From the shop to the drain — Volatile methylsiloxanes in cosmetics and personal care products

Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care products (PCPs), including creams and lotions, bath soaps, shampoo and hair care products to soften, smooth, and moisten. In fact, the intensive and widespread use of organosiloxanes combined with their lipophilic nature, makes them interesting targets for future research, particularly in the toxicology area.This study focused on determining the concentration levels of these compounds in the bestselling brands of PCPs in the Oporto region (Portugal), allowing the estimation of dermal and inhalation exposure to siloxanes and the evaluation of the quantities released to the environment “down-the-drain” and to air. To accomplish this task, a QuEChERS technique (“Quick, Easy, Cheap, Effective, Rugged, and Safe”) was employed to extract the siloxanes from the target PCPs, which has never been tested before. The resulting extract was analysed by gas chromatography–mass spectrometry (GC–MS). The limits of detection varied between 0.17 (L2) and 3.75 ng g^− 1 (L5), being much lower than any values reported in the literature for this kind of products. In general, satisfactory precision (< 10%) and accuracy values (average recovery of 84%) were obtained.123 PCPs were analysed (moisturizers, deodorants, body and hair washes, toilet soaps, toothpastes and shaving products) and volatile methylsiloxanes were detected in 96% of the samples, in concentrations between 0.003 μg g^− 1 and 1203 μg g^− 1. Shampoo exhibited the highest concentration for cyclic and aftershaves for linear siloxanes. Combining these results with the daily usage amounts, an average daily dermal exposure of 25.04 μg kg_bw^− 1 day^− 1 for adults and 0.35 μg kg_bw^− 1 day^− 1 for baby/children was estimated. The main contributors for adult dermal exposure were body moisturizers, followed by facial creams and aftershaves, while for babies/children were body moisturizers, followed by shower gel and shampoo. Similarly, the average daily inhalation exposure was also estimated. Values of 1.56 μg kg_bw^− 1 day^− 1 for adults and 0.03 μg kg_bw^− 1 day^− 1 for babies/children were calculated. An estimate of the siloxanes amount released “down-the-drain” into the sewage systems through the use of toiletries was also performed. An emission per capita between 49.25 and 9574 μg day^− 1 (mean: 1817 μg day^− 1) is expected and shampoo and shower gel presented the higher mean total values (1008 μg day^− 1 and 473.3 μg day^− 1, respectively). In the worst-case scenario, D5 and D3 were the predominant siloxanes in the effluents with 3336 μg day^− 1 and 3789 μg day^− 1, respectively. Regarding the air emissions per capita, values between 8.33 and 6109 μg day^− 1 (mean: 1607 μg day^− 1) are expected and D5 and D6 were the predominant siloxanes.     

Selective transfer of persistent organic pollutants and their metabolites in grey seals during lactation

Twenty grey seal (Halichoerus grypus) mother–pup pairs from the colony of the Isle of May (Scotland) were sampled at early and late lactation in order to study the transfer of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and their metabolites (HO-PCBs and HO-PBDEs) as well as organochlorine pesticides (OCPs), such as DDT and metabolites (DDXs) and hexachlorobenzene (HCB). The transfer of the naturally produced MeO-PBDEs was also investigated. Generally, concentrations (on a lipid weight basis) of the sum of PCBs, PBDEs and DDXs tended to be higher in all tissues at late lactation (for maternal outer blubber ΣPCBs = 3860 ± 2091 ng/g, ΣPBDEs = 120 ± 74 ng/g and ΣDDXs = 559 ± 207 ng/g; for maternal inner blubber ΣPCBs = 4229 ± 3274 ng/g, ΣPBDEs = 148 ± 118 ng/g and ΣDDXs = 704 ± 353 ng/g; for maternal serum ΣPCBs = 1271 ± 796 ng/g, ΣPBDEs = 27 ± 16 ng/g and ΣDDXs = 242 ± 125 ng/g; for milk ΣPCBs = 1190 ± 747 ng/g, ΣPBDEs = 55 ± 36 ng/g and ΣDDXs = 357 ± 160 ng/g; for pup serum ΣPCBs = 1451 ± 901 ng/g, ΣPBDEs = 48 ± 31 ng/g and ΣDDXs = 395 ± 201 ng/g). In all tissues, ΣMeO-PBDEs were found at very low levels or even undetected and their concentrations appeared to increase at late lactation only in maternal inner blubber (2.7 ± 1.3 to 5.3 ± 2.9 ng/g for early and late lactation, respectively) and milk (0.6 ± 0.3 to 1.1 ± 0.5 ng/g for early and late lactation, respectively). The transfer from inner blubber to maternal serum was selective and strongly depended on the log K_ow value of the compounds, with less lipophilic compounds being more efficiently released. Only a limited amount of HO-PCBs was transferred during lactation as 4-HO-CB-107 was the only metabolite detected in milk (29 to 40 pg/g lw). On the contrary, most of HO-PCB metabolites found in maternal serum were also detected in pup serum. These findings suggest not only a transplacental transfer of HO-PCBs from mothers to pups but also the possibility of endogenous biotransformation in suckling pups or accumulation of undetectable low amounts from milk.     

Are Chinese consumers at risk due to exposure to metals in crayfish? A bioaccessibility-adjusted probabilistic risk assessment

Freshwater crayfish, the world's third largest crustacean species, has been reported to accumulate high levels of metals, while the current knowledge of potential risk associated with crayfish consumption lags behind that of finfish. We provide the first estimate of human health risk associated with crayfish (Procambarus clarkii) consumption in China, the world's largest producer and consumer of crayfish. We performed Monte Carlo Simulation on a standard risk model parameterized with local data on metal concentrations, bioaccessibility (φ), crayfish consumption rate, and consumer body mass. Bioaccessibility of metals in crayfish was found to be variable (68–95%) and metal-specific, suggesting a potential influence of metal bioaccessibility on effective metal intake. However, sensitivity analysis suggested risk of metals via crayfish consumption was predominantly explained by consumption rate (explaining > 92% of total risk estimate variability), rather than metals concentration, bioaccessibility, or body mass. Mean metal concentrations (As, Cd, Cu, Ni, Pb, Se and Zn) in surveyed crayfish samples from 12 provinces in China conformed to national safety standards. However, risk calculation of φ-modified hazard quotient (HQ) and hazard index (HI) suggested that crayfish metals may pose a health risk for very high rate consumers, with a HI of over 24 for the highest rate consumers. Additionally, the φ-modified increased lifetime risk (ILTR) for carcinogenic effects due to the presence of As was above the acceptable level (10^− 5) for both the median (ILTR = 2.5 × 10^− 5) and 90th percentile (ILTR = 1.8 × 10^− 4), highlighting the relatively high risk of As in crayfish. Our results suggest a need to consider crayfish when assessing human dietary exposure to metals and associated health risks, especially for high crayfish-consuming populations, such as in China, USA and Sweden.     

The practical use of electrets in a public health radon remediation campaign

As part of a long-term assessment of domestic radon in Northamptonshire, England, a batch of 50 commercially available electrets was deployed for nearly 1000 exposures, individual exposure periods ranging from one to eight weeks. Responsivity was comparable with that of recently-calibrated Durridge RAD-7 continuously-monitoring equipment. Voltage history analysis indicated mean voltage decay during manufacturers' QA assessment of 0.059 ± 0.026 V day⁻¹, increasing to 0.114 ± 0.073 V day⁻¹ during storage to first use and to 0.204 ± 0.49 V day⁻¹ during inter-deployment storage. At a representative elevated radon concentration of 500 Bq m⁻³, the resulting perturbation is 3% over a 7-day deployment; at the typical mean Northamptonshire level of 80 Bq m⁻³ it approaches 22%. Each electret can be used for up to 25 measurements, which makes the technology attractive for organisational use. It is not suited for deployment by individual householders.     

Drugs of abuse and benzodiazepines in the Madrid Region (Central Spain): Seasonal variation in river waters,occurrence in tap water and potential environmental and human risk

This work analyzes the seasonal variation (winter and summer) of ten drugs of abuse, six metabolites and three benzodiazepines in surface waters from the Jarama and Manzanares Rivers in the Madrid Region, the most densely populated area in Spain. The occurrence of these compounds in tap water in this region is also investigated and a preliminary human health risk characterization performed for those substances found in tap water. Finally, a screening level risk assessment that combines the measured environmental concentrations (MECs) with dose–response data to estimate Hazard Quotients (HQs) for the compounds studied is also presented.The results of this study show the presence of fourteen out of the nineteen compounds analyzed in winter and twelve of them in summer. The most ubiquitous compounds, with a frequency of detection of 100% in both seasons, were the cocaine metabolite benzoylecgonine (BE), the amphetamine-type stimulant (ATS) ephedrine (EPH), the opioid methadone (METH), the METH metabolite 2-ethylene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), and the three benzodiazepines investigated, namely alprazolam (ALP), diazepam (DIA) and lorazepam (LOR). The highest concentrations observed corresponded to EPH (1020 ng L^− 1 in winter and 250 ng L^− 1 in summer). The only compounds not detected in both seasons were heroin (HER) and its metabolite 6-acetylmorphine (6ACM), lysergic acid diethylamide (LSD) and its metabolite 2-oxo-3-hydroxy-LSD (O-H-LSD), and Δ⁹-tetrahydrocannabinol (THC). In terms of overall concentration, all sampling points presented higher concentrations in winter than in summer. Statistical analyses performed to gather evidence concerning occasional seasonal differences in the concentrations of individual substances between summer and winter showed statistically significantly higher concentrations (p < 0.05) of BE, EPH and the opioid morphine (MOR) in winter than in summer. Two out of the nineteen compounds studied, namely cocaine (CO) and EPH, were detected in tap water from one sampling point at concentrations of 1.61 and 0.29 ng L^− 1, respectively. The preliminary human health risk characterization showed that no toxic effects could be expected at the detected concentration level in tap water.The screening level risk assessment showed that MOR, EDDP and the THC metabolite 11-nor-9-carboxy-Δ⁹-tetrahydrocannabinol (THC-COOH) were present in at least one of the sampling sites in a concentration leading to a Hazard Quotient (HQ) value between 1.0 and 10.0, thus indicating some possible adverse effects. The cumulative HQ or Toxic units (TUs) calculated for each of the groups studied showed that opioids and cannabinoids were present at concentrations high enough to potentially generate some adverse effects on at least one sampling point.     

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.