The bioavailability of selenium and risk assessment for human selenium poisoning in high-Se areas,China

Enshi prefecture of Hubei Province is well known for human selenium (Se) poisoning in the early 1960s in China. Sporadic cases of Se poisoning in livestocks are still being found. In this study, Se levels in water, cropland soils and various crops from high-Se areas of Enshi were measured to investigate the distribution and bioavailability of Se in the environments, as well as probable daily intake (PDI) of Se for local residents. The total Se in surface water ranged from 2.0 to 519.3 μg/L with a geometric mean of 46.0 ± 127.8 μg/L (n = 48), 70.5–99.5% of which was present in the form of Se(VI). The soil Se concentration varied from 2.89 to 87.3 μg/g with a geometric mean of 9.36 ± 18.6 μg/g (n = 45), and most of Se was associated with organic matter (OM-Se). The total Se in rice, corn, and vegetable samples were 2.11 ± 2.87 μg/g (n = 21), 3.76 ± 11.6 μg/g (n = 16), and 2.09 ± 3.38 μg/g (n = 25), respectively. Stream water Se is likely leached from carbonaceous shale and mine wastes, leading to Se accumulation in paddy soils. OM-Se may play an important role in Se uptake by rice plant in high-Se area of Enshi.The PDI of Se is approximately 2144 μg/day, and Se concentration in blood is estimated at about 3248 μg/L, posing a potential chronic Se poisoning risk to local residents. Cereal consumption (48.5%) makes a great contribution to human daily Se intake, followed by vegetables (36.6%), meats (8.5%), and drinking water (6.4%). However, when assessing health risk on human in high-Se areas, the contribution of drinking water to daily Se intake cannot be ignored due to high Se content and dominant Se(VI) species. Local inhabitants should be advised not to grow crops in high-Se lands or irrigate using high-Se water. If possible, they should drink pipe water and consume foods mixed with those from outside the high-Se areas.     

Boron exposure through drinking water during pregnancy and birth size

BackgroundBoron is a metalloid found at highly varying concentrations in soil and water. Experimental data indicate that boron is a developmental toxicant, but the few human toxicity data available concern mostly male reproduction.ObjectivesTo evaluate potential effects of boron exposure through drinking water on pregnancy outcomes.MethodsIn a mother-child cohort in northern Argentina (n = 194), 1–3 samples of serum, whole blood and urine were collected per woman during pregnancy and analyzed for boron and other elements to which exposure occurred, using inductively coupled plasma mass spectrometry. Infant weight, length and head circumference were measured at birth.ResultsDrinking water boron ranged 377–10,929 μg/L. The serum boron concentrations during pregnancy ranged 0.73–605 μg/L (median 133 μg/L) and correlated strongly with whole-blood and urinary boron, and, to a lesser extent, with water boron. In multivariable-adjusted linear spline regression analysis (non-linear association), we found that serum boron concentrations above 80 μg/L were inversely associated with birth length (B − 0.69 cm, 95% CI − 1.4; − 0.024, p = 0.043, per 100 μg/L increase in serum boron). The impact of boron appeared stronger when we restricted the exposure to the third trimester, when the serum boron concentrations were the highest (0.73–447 μg/L). An increase in serum boron of 100 μg/L in the third trimester corresponded to 0.9 cm shorter and 120 g lighter newborns (p = 0.001 and 0.021, respectively).ConclusionsConsidering that elevated boron concentrations in drinking water are common in many areas of the world, although more screening is warranted, our novel findings warrant additional research on early-life exposure in other populations.     

Uranium in drinking-water: A unique case of guideline value increases and discrepancies between chemical and radiochemical guidelines

BackgroundUranium represents a unique case for an element naturally present in the environment, as its chemical guideline value in drinking water significantly increased from 2 μg/L in 1998 up to 15 μg/L in 2004 and then to 30 μg/L in 2011, to date corresponding to a multiplication factor of 15 within a period of just 13 years.ObjectivesIn this commentary we summarize the evolution of uranium guideline values in drinking-water based on both radiological and chemical aspects, emphasizing the benefit of human studies and their contribution to recent recommendations. We also propose a simpler and better consistency between radiological and chemical values.DiscussionThe current chemical guideline value of 30 μg/L is still designated as provisional because of scientific uncertainties regarding uranium toxicity. During the same period, the radiological guideline for ²³⁸U increased from 4 Bq/L to 10 Bq/L while that for ²³⁴U decreased from 4 Bq/L to 1 Bq/L. These discrepancies are discussed here, and a value of 1 Bq/L for all uranium isotopes is proposed to be more consistent with the current chemical value of 30 μg/L.ConclusionContinuous progress in the domains of toxicology and speciation should enable a better interpretation of the biological effects of uranium in correlation with epidemiological human studies. This will certainly aid future proposals for uranium guideline values.     

The national trend of blood lead levels among Chinese children aged 0–18 years old, 1990–2012

We analyzed the epidemiological data during 1990–2012 that investigated the blood lead level (BLL) in the population aged 0–18 years old in China mainland and provided evidence of the benefits of implementing policies to prevent lead pollution based on the dynamic changes of BLL. Data were collected through databases including China Knowledge Resource Integrated Database (CNKI), CBM disc, Wanfang Data, Pubmed and Medline. The inclusion criteria were: 1. Epidemiological study in healthy population not included studies limited to specific patient; 2. Study subject was not the specific lead exposure population; 3. Sample size should be no less than 100 (for neonatal, no less than 50); 4. BLL detection was under strict quality control; and 5. Results should be presented as BLL (arithmetic mean level or geometric mean level). 62 articles were included in this study. All the surveys in these articles contained 189,352 subjects in 19 provinces, autonomous regions and municipalities. Linear regression analysis showed a significant decrease between 1990 and 2012 with an estimated regression coefficient of 3.05/year (SE = 0.01, p < 0.001). BLL gradually declined since early 21st century. Median levels of BLL among the three economic zones were 51.4 μg/L in the eastern zone, 52.72 μg/L in the central zone and 46.2 μg/L in the western zone respectively. Median BLLs in male and female population aged 0–18 years old of China were 48.8 μg/L and 46.1 μg/L. Median levels of BLL among the different age ranges were 74.9 μg/L in newborn, 46.4 μg/L in 0 to 3 years old, 57.6 μg/L in 3 to 7 years old and 55.6 μg/L in above 7 years old respectively. In conclusion, the BLL in the Chinese population of 0–18 years old has gradually dropped in the past 10 years. The decline in temporal trend still remains under potential impacts of several factors such as economical level, gender and age difference. Although, China has made significant achievements in the control prevention of lead pollution, concerted efforts are still warranted to reduce children lead poisoning.     

Elevated childhood exposure to arsenic despite reduced drinking water concentrations — A longitudinal cohort study in rural Bangladesh

ObjectivesThe aim of this study was to evaluate the massive efforts to lower water arsenic concentrations in Bangladesh.MethodsIn our large mother–child cohort in rural Matlab, we measured the arsenic concentrations (and other elements) in drinking water and evaluated the actual exposure (urinary arsenic), from early gestation to 10 years of age (n = 1017).ResultsMedian drinking water arsenic decreased from 23 (2002–2003) to < 2 μg/L (2013), and the fraction of wells exceeding the national standard (50 μg/L) decreased from 58 to 27%. Still, some children had higher water arsenic at 10 years than earlier. Installation of deeper wells (> 50 m) explained much of the lower water arsenic concentrations, but increased the manganese concentrations. The highest manganese concentrations (~ 900 μg/L) appeared in 50–100 m wells. Low arsenic and manganese concentrations (17% of the children) occurred mainly in > 100 m wells. The decrease in urinary arsenic concentrations over time was less apparent, from 82 to 58 μg/L, indicating remaining sources of exposure, probably through food (mean 133 μg/kg in rice).ConclusionDespite decreased water arsenic concentrations in rural Bangladesh, the children still have elevated exposure, largely from food. Considering the known risks of severe health effects in children, additional mitigation strategies are needed.     

Novel exposure biomarkers of N,N-diethyl-m-toluamide (DEET): Data from the 2007–2010 National Health and Nutrition Examination Survey

BackgroundN,N-diethyl-m-toluamide (DEET) is a widely used insect repellent in the United States.ObjectivesTo assess exposure to DEET in a representative sample of persons 6 years and older in the U.S. general population from the 2007–2010 National Health and Nutrition Examination Survey.MethodsWe analyzed 5348 urine samples by using online solid-phase extraction coupled to isotope dilution-high-performance liquid chromatography-tandem mass spectrometry. We used regression models to examine associations of various demographic parameters with urinary concentrations of DEET biomarkers.ResultsWe detected DEET in ~ 3% of samples and at concentration ranges (> 0.08 μg/L–45.1 μg/L) much lower than those of 3-(diethylcarbamoyl)benzoic acid (DCBA) (> 0.48 μg/L–30,400 μg/L) and N,N-diethyl-3-hydroxymethylbenzamide (DHMB) (> 0.09 μg/L–332 μg/L). DCBA was the most frequently detected metabolite (~ 84%). Regardless of survey cycle and the person's race/ethnicity or income, adjusted geometric mean concentrations of DCBA were higher in May–Sep than in Oct–Apr. Furthermore, non-Hispanic whites in the warm season were more likely than in the colder months [adjusted odds ratio (OR) = 10.83; 95% confidence interval (CI), 3.28–35.79] and more likely than non-Hispanic blacks (OR = 3.45; 95% CI, 1.51–7.87) to have DCBA concentrations above the 95th percentile.ConclusionsThe general U.S. population, including school-age children, is exposed to DEET. However, reliance on DEET as the sole urinary biomarker would likely underestimate the prevalence of exposure. Instead, oxidative metabolites of DEET are the most adequate exposure biomarkers. Differences by season of the year based on demographic variables including race/ethnicity likely reflect different lifestyle uses of DEET-containing products.     

Environmental exposure to lithium during pregnancy and fetal size: A longitudinal study in the Argentinean Andes

BackgroundLithium, used for treating bipolar disease, crosses freely the placenta and is classified as teratogenic. It is unclear to what extent environmental lithium exposure may affect fetal growth and development.ObjectivesTo elucidate potential effects of lithium exposure through drinking water during pregnancy on fetal size.MethodsWe developed a prospective population-based mother–child cohort (N = 194) in an area with highly varying drinking water lithium concentrations (5-1600 μg/L) in northern Argentinean Andes. Blood and urinary lithium concentrations (sampled repeatedly during pregnancy) were measured using inductively coupled plasma mass spectrometry. We measured fetal size by ultrasound in second and third trimesters, and weight, length and head circumference at birth. Multivariable models were used to examine associations between lithium exposure (continuous and in tertiles) and fetal size measures.ResultsLithium in maternal blood (median 25; range 1.9–145 μg/L) and urine (1645; 105–4600 μg/L) was inversely associated (apparently linearly) with all fetal measures (body, head and femur) in the second trimester, and with birth length (β − 0.53 cm per 25 μg/L increase in blood lithium, 95%CI − 1.0; − 0.052). An increase of 100 μg/L in blood was associated with 2 cm shorter newborns (about one standard deviation).ConclusionsLithium exposure through drinking water was associated with impaired fetal size and this seemed to be initiated in early gestation. Further studies are warranted to confirm causality and to understand the mechanisms. If confirmed, these findings have public health relevance and emphasize the need for more data on lithium concentrations in drinking water, including bottled water.     

Urinary concentrations of organophosphate and carbamate pesticides in residents of a vegetarian community

Few population studies have measured urinary levels of pesticides in individuals with vegan, vegetarian, or organic diets. The objectives of this study were to evaluate whether a vegan/vegetarian diet was associated with increased exposure to organophosphate and carbamate pesticides, and to evaluate the impact of organic consumption on pesticide exposure in vegans and vegetarians. In the current pilot study conducted in 2013–2014, we collected spot urine samples and detailed 24 h recall dietary data in 42 adult residents of Amirim, a vegetarian community in Northern Israel. We measured urinary levels of non-specific organophosphate pesticide metabolites (dialkylphosphates, (DAPs)) and specific metabolites of the current-use pesticides chlorpyrifos (3,5,6-trichloro-2-pyridinol (TCPy)), propoxur (-isopropoxyphenol (IPPX)), and carbaryl (1-naphthol). Six DAP metabolites were detected in between 67 and 100% of urine samples, with highest geometric mean concentrations for dimethylphosphate (19.2 μg/g). Creatinine-adjusted median concentrations of total DAPs and of TCPy were significantly higher in Amirim residents compared to the general Jewish population in Israel (0.29 μmol/g compared to 0.16, p < 0.05 for DAPs and 4.32 μg/g compared to 2.34 μg/g, p < 0.05 for TCPy). Within Amirim residents, we observed a positive association between vegetable intake and urinary TCPy levels (rho = 0.47, p < 0.05) and lower median total dimethyl phosphate levels in individuals reporting that > 25% of the produce they consume is organic (0.065 μmol/L compared to 0.22, p < 0.05). Results from this pilot study indicate relatively high levels of urinary organophosphate pesticide metabolite concentrations in residents of a vegetarian community, a positive association between vegetable intake and urinary levels of a chlorpyrifos specific metabolite, and lower levels of total dimethyl phosphate in individuals reporting higher intake of organic produce. Results suggest that consumption of organic produce may offer some protection from increased exposure to organophosphate pesticide residues in vegetarians.     

Organophosphate pesticide exposure and perinatal outcomes in Shanghai,China

Although pesticide use is widespread in China, little is known about levels of exposure to organophosphate pesticides in the population and its potential adverse health effects. We investigated levels of organophosphate exposure in pregnant women and the association between organophosphate exposure and perinatal outcomes in Shanghai, China, by enrolling 187 healthy pregnant women between September 2006 and January 2007. Pesticide exposure was assessed by a questionnaire administered to the mothers in the hospital after delivery as well as by analyses of maternal urinary nonspecific metabolites of organophosphate pesticides (dimethyl and diethyl phosphates). Information on birth weight and length was collected from medical records. Geometric means of metabolites were 25.75 μg/L for dimethylphosphate (DMP); 11.99 μg/L for dimethylthiophosphate (DMTP); 9.03 μg/L for diethylphosphate (DEP); and 9.45 μg/L for diethyldithiophosphate (DETP). We found that a log unit increase in urinary DEP was associated with a decrease in gestational duration in girls by 1.79 weeks. [ß_adjusted = − 1.79 weeks per log₁₀ unit increase; 95% confidence interval (CI), −2.82 to − 0.76; p = 0.001]. These data suggest that high pesticide level might adversely affect duration of gestation although this association was not present among boys. No associations for any of the organophosphate exposure measures were present for birth weight and length, suggesting that organophosphate pesticides may have no effects on fetal growth. Given that maternal urine pesticide levels in Shanghai were much higher than those reported in developed countries, more studies on the effects of in utero organophosphate exposure on fetal growth and child neurodevelopment are warranted.     

Selenium exposure in subjects living in areas with high selenium concentrated drinking water: Results of a French integrated exposure assessment survey

BackgroundSelenium is an essential element which can be toxic if ingested in excessive quantities. The main human exposure is food. In addition, intake may be boosted by consumption drinking water containing unusual high selenium concentration.ObjectiveWe measured the individual selenium level of people exposed to selenium concentration in drinking water greater than the maximum recommended limit which is 10 μg/L.MethodsWe carried out a prospective cohort study on 80 adults (40 exposed subjects i.e. living in the involved area and 40 non-exposed ones i.e. living elsewhere) in western France. We used three different approaches: (1) direct measurement of ingested selenium by the duplicate portion method, (2) dietary reconstitution with a food frequency questionnaire (FFQ) and (3) evaluation of the individual selenium status by measuring the selenium content in toenail clippings. Analyses were performed by inductively coupled plasma-mass spectrometry. The association between toenail selenium concentration and area of residence was analyzed using linear regression with repeated measurements.ResultsWe estimated selenium intake from FFQ at 64 ± 14 μg/day for exposed subjects as opposed to 52 ± 14 μg/day for the non-exposed ones. On the basis of 305 duplicate diet samples, average intake was estimated at 64 ± 26 μg/day for exposed subjects. Area of residence (p = 0.0030) and smoking (p = 0.0054) were independently associated with toenail selenium concentration.ConclusionWhatever method used for estimating selenium intake, the selenium level in this studied area with high selenium concentrated drinking water is much lower than in seleniferous areas.     

Plasma levels of selenium-containing proteins in Inuit adults from Nunavik

Selenium (Se) is highly abundant in marine foods traditionally consumed by Inuit of Nunavik (Northern Quebec, Canada) and accordingly, their Se intake is among the highest in the world. However, little is known regarding the biological implications of this high Se status in this Arctic indigenous population. We used a method combining affinity chromatography and inductively coupled plasma-mass spectrometry with quantification by post-column isotope dilution to determine total Se levels and concentrations of Se-containing proteins in archived plasma samples of Inuit adults who participated to the 2004 Nunavik Inuit Health Survey (N = 852). Amounts of mercury (Hg) associated with Se-containing proteins were also quantified. Results show that glutathione peroxidase 3 (GPx3), selenoprotein P (SelP) and selenoalbumin (SeAlb) represented respectively 25%, 52% and 23% of total plasma Se concentrations. In addition, small amounts of Hg co-eluted with each Se-containing protein and up to 50% of plasma Hg was associated to SelP. Total plasma Se concentrations (median = 139 μg L^− 1; interquartile range (IQR) = 22.7 μg L^− 1) were markedly lower and less variable than whole blood Se concentration (median = 261 μg L^− 1, IQR = 166 μg L^− 1). A non linear relation was observed between whole blood Se and plasma Se levels, with plasma Se concentrations leveling off at approximately 200 μg L^− 1, whereas 16% and 3% of individuals exhibited whole blood concentrations higher than 500 μg L^− 1 and 1000 μg L^− 1, respectively. In contrast, a linear relationship was previously reported in communities consuming Brazil nuts which are rich Se, mainly present as selenomethionine. This suggests that a different selenocompound, possibly selenoneine, is present in the Arctic marine food chain and accumulates in the blood cellular fraction of Inuit.     

Blood cadmium,mercury, and lead in children: An international comparison of cities in six European countries,and China,Ecuador, and Morocco

Children's blood-lead concentration (B-Pb) is well studied, but little is known about cadmium (B-Cd) and mercury (B-Hg), in particular for central Europe. Such information is necessary for risk assessment and management. Therefore, we here describe and compare B-Pb, B-Cd and B-Hg in children in six European, and three non-European cities, and identify determinants of these exposures. About 50 school children (7–14 years) from each city were recruited (totally 433) in 2007–2008. Interview and questionnaire data were obtained. A blood sample was analyzed: only two laboratories with strict quality control were used. The European cities showed only minor differences for B-Cd (geometric means 0.11–0.17 μg/L) and B-Pb (14–20 μg/L), but larger for B-Hg (0.12–0.94 μg/L). Corresponding means for the non-European countries were 0.21–0.26, 32–71, and 0.3–3.2 μg/L, respectively. For B-Cd in European samples, traffic intensity close to home was a statistically significant determinant, for B-Hg fish consumption and amalgam fillings, and for B-Pb sex (boys higher). This study shows that European city children's B-Cd and B-Pb vary only little between countries; B-Hg differs considerably, due to varying tooth restoration practices and fish intake. Traffic intensity seemed to be a determinant for B-Cd. The metal concentrations were low from a risk perspective but the chosen non-European cities showed higher concentrations than the cities in Europe.     

Mercury and thyroid autoantibodies in U.S. women,NHANES 2007–2008

Associations between positive thyroid autoantibodies and total blood mercury in women were evaluated using the National Health and Nutrition Examination Survey (NHANES), 2007–2008. Women are at increased risk for autoimmune disorders, mercury exposure has been associated with cellular autoimmunity and mercury accumulates in the thyroid gland. We used multiple logistic regression to evaluate the associations between total bloodmercury and thyroglobulin autoantibody antibody positivity and thyroid peroxidase autoantibody positivity in non-pregnant, non-lactating women aged 20 and older not currently using birth control pills or other hormone therapies, adjusted for demographic factors, menopausal status, nutrient intake and urine iodine (n = 2047). Relative to women with the lowest mercury levels (≤ 0.40 μg/L), women with mercury > 1.81 μg/L (upper quintile) showed 2.24 (95% CI = 1.22, 4.12) greater odds for thyroglobulin autoantibody positivity (p_trend = 0.032); this relationship was not evident for thyroid peroxidase autoantibody positivity. Results suggest an association between mercury and thyroglobulin autoantibody positivity.     

Prenatal methylmercury exposure and language delay at three years of age in the Norwegian Mother and Child Cohort Study

Prenatal methylmercury (MeHg) exposure and its possible neurodevelopmental effects in susceptible children are of concern. Studies of MeHg exposure and negative health outcomes have shown conflicting results and it has been suggested that co-exposure to other contaminants and/or nutrients in fish may confound the effect of MeHg. Our objective was to examine the association between prenatal exposure to MeHg and language and communication development at three years, adjusting for intake of fish, n − 3 long chain polyunsaturated fatty acids (n − 3 LCPUFAs) and co-exposure to dioxins and dioxin like polychlorinated biphenyls (dl-PCBs).We used data from the Norwegian Mother and Child Cohort Study (MoBa) collected between 2002 and 2008. The study sample consisted of 46,750 mother-child pairs. MeHg exposure was calculated from reported fish intake during pregnancy by a FFQ in mid-pregnancy. Children's language and communication skills were measured by maternal report on the Dale and Bishop grammar rating and the Ages and Stages communication scale (ASQ). We estimated odds ratios (OR) and 95% confidence intervals (CI) using logistic regressions.Median MeHg exposure was 1.3 μg/day, corresponding to 0.14 μg/kg bw/week. An exposure level above the 90th percentile (> 2.6 μg/day, > 0.29 μg/kg bw/week) was defined as the high MeHg exposure. Results indicated an association between high MeHg exposure and unintelligible speech with an adjusted OR 2.22 (1.31, 3.72). High MeHg exposure was also associated with weaker communication skills adjusted OR 1.33 (1.03, 1.70). Additional adjustment for fish intake strengthened the associations, while adjusting for PCBs and n − 3 LCPUFA from diet or from supplements had minor impact. In conclusion, significant associations were found between prenatal MeHg exposure above the 90th percentile and delayed language and communication skills in a generally low exposed population.     

Associations between polycyclic aromatic hydrocarbon (PAH) exposure and oxidative stress in people living near e-waste recycling facilities in China

Emission of polycyclic aromatic hydrocarbons (PAHs) from e-waste recycling activities in China is known. However, little is known on the association between PAH exposure and oxidative damage to DNA and lipid content in people living near e-waste dismantling sites. In this study, ten hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) and two biomarkers [8-hydroxy-2′-deoxyguanosine (8-OHdG) and malondialdehyde (MDA)] of oxidative stress were investigated in urine samples collected from people living in and around e-waste dismantling facilities, and in reference population from rural and urban areas in China. The urinary levels of ∑₁₀OH-PAHs determined in e-waste recycling area (GM: 25.4 μg/g Cre) were significantly higher (p < 0.05) than those found in both rural (11.7 μg/g Cre) and urban (10.9 μg/g Cre) reference areas. The occupationally exposed e-waste workers (36.6 μg/g Cre) showed significantly higher (p < 0.01) urinary Σ₁₀OH-PAHs concentrations than non-occupationally exposed people (23.2 μg/g Cre) living in the e-waste recycling site. The differences in urinary Σ₁₀OH-PAHs levels between smokers (23.4 μg/g Cre) and non-smokers (24.7 μg/g Cre) were not significant (p > 0.05) in e-waste dismantling sites, while these differences were significant (p < 0.05) in rural and urban reference areas; this indicated that smoking is not associated with elevated levels of PAH exposure in e-waste dismantling site. Furthermore, we found that urinary concentrations of Σ₁₀OH-PAHs and individual OH-PAHs were significantly associated with elevated 8-OHdG, in samples collected from e-waste dismantling site; the levels of urinary 1-hydroxypyrene (1-PYR) (r = 0.284, p < 0.01) was significantly positively associated with MDA. Our results indicate that the exposure to PAHs at the e-waste dismantling site may have an effect on oxidative damage to DNA among selected participants, but this needs to be validated in large studies.     

The influence of size on the toxicity of an encapsulated pesticide: a comparison of micron- and nano-sized capsules

Encapsulation technology involves entrapping a chemical active ingredient (a.i.) inside a hollow polymeric shell and has been applied to commercial pesticide manufacturing for years to produce capsule suspension (CS) formulations with average particle sizes in the micron-scale. The few literature sources that investigate the environmental fate and toxicity to non-target organisms of encapsulated commercially available pesticide products with regard to capsule size report on average sizes between 20 and 50 μm. Here, we have identified a CS formulation with an average capsule size of approximately 2 μm with some capsules extending into the nanometer scale (~ 200 nm). Determining how carrier size influences toxicity is important to understanding if current pesticide risk assessments are sufficient to protect against products that incorporate encapsulation technology. Here, a commercial pyrethroid CS pesticide with lambda-cyhalothrin (λ-Cy) as the a.i. was separated into two suspensions, a fraction consisting of nano-sized capsules (~ 250 nm) and a fraction of micron-sized capsules (~ 2200 nm) in order to investigate the influence of capsule size on toxicity to embryonic zebrafish, Danio rerio. Toxicity was evaluated 24 h after exposure to equivalent amounts of a.i. by the presence and severity of pyrethroid-specific tremors, 14 sublethal developmental impacts and mortality. Fish exposed to greater than 20 μg a.i. L^− 1 technical λ-Cy or formulated product experienced curvature of the body axis, pericardial edema, craniofacial malformations, and mortality. Exposure to the unfractionated formulation, micro fraction, nano fraction and technical a.i. resulted in no significant differences in the occurrence of sublethal impacts or mortality; however, the technical a.i. exposure resulted in significantly less fish experiencing tremors and shorter tremors compared to any of the formulated product exposures. This suggests that the capsule size does not influence the toxic response of the entrapped λ-Cy, but the presence or absence of the capsules does. Testing across other encapsulated products is needed to determine if size does not have influence on toxicity regardless of encapsulation technology.     

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.     

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.     

Cleaning-induced arsenic mobilization and chromium oxidation from CCA-wood deck: Potential risk to children

Concern about children's exposure to arsenic (As) from wood treated with chromated-copper-arsenate (CCA) led to its withdrawal from residential use in 2004. However, due to its effectiveness, millions of American homes still have CCA-wood decks on which children play. This study evaluated the effects of three deck-cleaning methods on formation of dislodgeable As and hexavalent chromium (CrVI) on CCA-wood surfaces and in leachate. Initial wipes from CCA-wood wetted with water showed 3–4 times more dislodgeable As than on dry wood. After cleaning with a bleach solution, 9.8–40.3 μg/100 cm² of CrVI was found on the wood surface, with up to 170 μg/L CrVI in the leachate. Depending on the cleaning method, 699–2473 mg of As would be released into the environment from cleaning a 18.6-m²-deck. Estimated As doses in children aged 1–6 after 1 h of playing on a wet CCA-wood deck were 0.25–0.41 μg/kg. This is the first study to identify increased dislodgeable As on wet CCA-wood and to evaluate dislodgeable CrVI after bleach application. Our data suggest that As and CrVI in 25-year old CCA-wood still show exposure risks for children and potential for soil contamination.     

The contribution of diet to total bisphenol A body burden in humans: Results of a 48 hour fasting study

Human biomonitoring studies measuring bisphenol A (BPA) in urine have shown widespread exposure in the general population. Diet is thought to be a major route of exposure. We studied urinary BPA patterns in five individuals over a 48-h period of fasting (bottled water only). Personal activity patterns were recorded with a diary to investigate non-dietary routes of exposure. All urine void events during the fast were collected, as well as events before and after the fast. The pattern of BPA concentrations was similar for all participants: they rose near the beginning of the fast (after the pre-fast meal), declined over the next 24 h, fluctuated at lower levels during the second day, and then rose after the post-fast meal. Concentrations (~ 2 μg/g creatine) and calculated BPA intakes (~ 0.03 μg/kg-day) in these individuals during the first 24 h were consistent with general population exposures. For the second 24 h, concentrations and intakes declined by about two-thirds. One of the individuals had an extraordinary pre-fast exposure event with concentrations rising as high as 98 μg/g creatine but declining to < 5 μg/g creatine by day 2. Given patterns found in day 1 and the subsequent decline to lower levels in day 2, we hypothesize that BPA exposures in these individuals were diet-driven. No events in the diary (use of personal care products, e.g.) appear associated with exposures. On day 2, non-dietary sources may still be present, such as from dust. Another hypothesis is that small reservoirs of BPA from past exposures are released from storage (lipid reservoirs, e.g.) and excreted.