Gamma Radioactivity Detection Limits and Associated Radionuclide Intakes Study in Artificial Human Urine Using Sodium-iodide and High-purity Germanium Detectors.

ABSTRACT: The performance of several gamma detectors was investigated for emergency urine bioassay screening of two radionuclides of concern: 131 I and 137 Cs. Unspiked artificial urine samples were measured for 10 min each on four different gamma detectors: 80% relative efficiency high-purity Ge detector in standard shielding, 102% low-background high-purity Ge detector equipped with top muon shield, 78% high-purity Ge well detector in standard shielding, and 4″ × 4″ NaI well detector in standard shielding. The measured gamma spectra were analyzed in two ways: (1) for the 364-keV peak region of 131 I and 662-keV peak region of 137 Cs and (2) for the total counts in the full energy spectrum (50-2,048 keV). The results were analyzed using the principles of signal detection theory according to the Currie's formalism extended by a complete uncertainty propagation. This enabled calculation of the detection capability in terms of detection limit (Bq L -1 ) of urine, the latter referred to as minimum detectable activity. The NaI well detector had the lowest minimum detectable activities for total spectra, whereas the high-purity Ge well detector had the lowest peak minimum detectable activity values. Minimum detectable inhalation and ingestion intakes from urine bioassay were calculated from the minimum detectable activity values for urine collection 1 d, 1 wk, and 1 mo past the initial intake. The calculated intakes were compared with annual limits on intake. The results are interpreted with respect to a large-scale radiological emergency response.

Human biomonitoring reference values for some non-persistent chemicals in blood and urine derived from the Canadian Health Measures Survey 2009-2013.

The Canadian Health Measures Survey collects nationally representative human biomonitoring data on a suite of chemicals and their metabolites, including many non-persistent chemicals. Data has been collected on non-persistent chemicals, including acrylamide, chlorophenols, environmental phenols and triclocarban, organophosphate insecticides, phthalates, polycyclic aromatic hydrocarbon, pyrethroid insecticides, and volatile organic compounds from 2009 to 2013. Using a systematic approach building on the reference interval concept proposed by the International Federation of Clinical Chemistry and Laboratory Medicine and the International Union of Pure and Applied Chemistry, we derive human biomonitoring reference values (RV95s) for these classes of non-persistent chemicals in blood and urine for the general Canadian population. RV95s were derived for biomarkers of non-persistent chemicals with widespread detection in Canadians (>66% detection rate). Samples with urinary creatinine levels outside the recommended range of 0.3-3.0 µg/L were excluded. Reference populations were constructed by applying smoking and fasting as exclusion criteria where appropriate. Age and sex were evaluated as possible partitioning criteria and separate RV95s were derived for sub-populations in cases where partitioning was deemed necessary. Reference values were derived for 40 biomarkers and represent the first set of RV95s for non-persistent chemicals in the general Canadian population. These values provide a measure of the upper margin of background exposure in the general population and can be compared against individual and population human biomonitoring data. RV95s can be used to by public health officials to identify individuals with high exposures, and by risk assessors and risk managers to identify atypical exposures or subpopulations with elevated exposures.

Human biomonitoring reference values derived for persistent organic pollutants in blood plasma from the Canadian Health Measures Survey 2007-2011.

Nationally representative human biomonitoring data on persistent organic pollutants (POPs) including organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs) brominated flame retardants (BFRs) and perfluoroalkyl substances (PFASs) are available through the Canadian Health Measures Survey (CHMS). We have used a systematic approach building on the reference interval concept proposed by the International Federation of Clinical Chemistry and Laboratory Medicine and the International Union of Pure and Applied Chemistry to derive human biomonitoring reference values (RV95s) for selected POPs in blood plasma in the general Canadian population. Biomarkers were chosen based on specific selection criteria including their detection in most Canadians (>66% detection rate). Age and sex were evaluated as possible partitioning criteria and separate RV95s were derived for the sub-populations in cases where partitioning was deemed necessary. RV95s for OCs, PCBs, and BFRs were derived both on a whole weight of blood plasma and on a lipid weight adjusted basis whereas they were derived only on a whole weight basis for PFASs. RV95s ranged from 0.018µg/L (PCB 201) to 21µg/L (perfluorooctane sulfonate) and from 3.1µg/kg lipid (PCB 201) to 1400µg/kg lipid (p,p'-DDE). The 22 RV95s reported in this paper represent the first set of reference values for POPs in the Canadian general population against which individual and population human biomonitoring data may be compared.

An overview of human biomonitoring of environmental chemicals in the Canadian Health Measures Survey: 2007-2019.

Human biomonitoring (HBM) is used to indicate and quantify exposure by measuring environmental chemicals, their metabolites or reaction products in biological specimens. The biomonitoring component of the Canadian Health Measures Survey (CHMS) is the most comprehensive initiative providing general population HBM data in Canada. The CHMS is an ongoing cross-sectional direct measures survey implemented in 2-year cycles. It provides nationally-representative data on health, nutritional status, environmental exposures, and related risks and protective characteristics. The survey follows a robust planning, design and sampling protocol as well as a comprehensive quality assurance and quality control regime implemented for all aspect of the survey to ensure the validity of the HBM results. HBM blood and urine data are available for CHMS cycles 1 (2007-2009), 2 (2009-2011) and 3 (2012-2013). Field collection has been completed for cycle 4 (2014-2015), with cycle 5 (2016-2017) in progress and cycle 6 planning (2018-2019) being finalized. Biomonitoring results for 279 chemicals are expected over the six cycles of the CHMS (220 in individual blood, urine or hair samples, and 59 in pooled serum samples). The chemicals include metals and trace elements, polychlorinated biphenyls (PCBs), organochlorines, flame retardants, perfluoroalkyl substances, volatile organic compounds (VOCs) and metabolites, environmental phenols, triclocarban, acrylamide, pesticides (e.g., triazines, carbamates, organophosphates, phenoxy, pyrethroids) and/or their metabolites, chlorophenols, polycyclic aromatic hydrocarbon (PAH) metabolites, phthalates and alternate plasticizer metabolites, and tobacco biomarkers. Approximately one half of the chemicals measured in individual blood and urine samples over the first three cycles were detected in more than 60% of samples. CHMS biomonitoring data have been used to establish baseline HBM concentrations in Canadians; inform public health, regulatory risk assessment and management decisions; and fulfil national and international reporting requirements. Concurrent efforts are underway in Canada to develop statistically- and risk-based concepts and tools to interpret biomonitoring data.

Human biomonitoring reference values for metals and trace elements in blood and urine derived from the Canadian Health Measures Survey 2007-2013.

Human biomonitoring reference values are statistical estimates that indicate the upper margin of background exposure to a given chemical at a given time. Nationally representative human biomonitoring data on 176 chemicals, including several metals and trace elements, are available in Canada from 2007 to 2013 through the Canadian Health Measures Survey (CHMS). In this work, we used a systematic approach based on the reference interval concept proposed by the International Federation of Clinical Chemistry and Laboratory Medicine and the International Union of Pure and Applied Chemistry to derive reference values (RV95s) for metals and trace elements. These RV95s were derived for blood and urine matrices in the general Canadian population based on the latest biomonitoring data from the CHMS. Biomarkers were chosen based on specific selection criteria, including widespread detection in Canadians (≥66% detection rate). Reference populations were created for each biomarker by applying appropriate exclusion criteria. Age and sex were evaluated as possible partitioning criteria and separate RV95s were derived for the sub-populations in cases where partitioning was deemed necessary. The RV95s for metals and trace elements in blood ranged from 0.18µg/L for cadmium in young children aged 3-5 years to 7900µg/L for zinc in males aged 20-79 years. In the case of urinary biomarkers, the RV95s ranged from 0.17µg/L for antimony in the total population aged 3-79 years to 1400mg/L for fluoride in adults aged 20-79 years. These RV95s represent the first set of reference values for metals and trace elements in the general Canadian population. We compare the RV95s from other countries where available and discuss factors that could influence such comparisons.

Concentrations of persistent organic pollutants in maternal and cord blood from the maternal-infant research on environmental chemicals (MIREC) cohort study.

BACKGROUND: Pregnant women are an especially important population to monitor for environmental exposures given the vulnerability of the developing fetus. During pregnancy and lactation chemical body burdens may change due to the significant physiological changes that occur. Developmental exposures to some persistent organic pollutants (POPs) have been linked with adverse health outcomes. METHODS: First trimester maternal and cord blood plasma concentrations of several POPs including polychlorinated biphenyls (PCBs), organochlorine pesticides (OCs), polybrominated diphenyl ethers (PBDE)s and perfluoroalkyl substances (PFASs) were measured in samples from 1983 pregnant women enrolled in the Maternal-Infant Research on Environmental Chemicals (MIREC) cohort. Predictors of exposure were also identified. RESULTS: In maternal plasma, there was >90 % detection for the perfluoroalkyl substances (PFASs) perfluorooctanoic acid (PFOA), perfluoroctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), and dichlorodiphenyldichloroethylene (DDE), oxychlordane and PCB 138 and 153. Cord blood plasma had much lower detection rates with low or very limited detection for most PCBs and PBDEs. The PFASs were the most frequently detected (23-64 %) chemical class in cord plasma. In a subset of 1st and 3rd trimester paired samples, PFAS concentrations were found to be strongly correlated and had ICCs ranging from 0.64 (PFOA) to 0.83 (PFHxS). The cord:maternal plasma concentration ratios ranged from 0.14 (PFOS) to 0.87 (oxychlordane, lipid adjusted). Similar to other studies, we found parity, maternal age, income, education, smoking status, pre-pregnancy BMI and fish consumption to be significant predictors for most chemicals. Those participants who were foreign-born had significantly higher concentrations of organochlorinated pesticides and PCBs. CONCLUSIONS: In the MIREC study, multiple chemical contaminants were quantified in the plasma of pregnant women. In cord plasma PFOA had the highest detection rate. However, compared to other Canadian and international population studies, the MIREC participants had lower contaminant concentrations of these substances.

Long-term monitoring of radioactivity in fish from New York waters.

As part of an environmental surveillance program operated by the New York State (NYS) Department of Health, measurements of various radionuclides in aquatic life (primarily fish) collected from waterways in NYS have occurred for decades. An investigation was undertaken to gain a better understanding of the occurrence, activity levels, and extent of radionuclide variations in aquatic life obtained from local waterways in relation to concentrations reported in fish from sites outside NYS (e.g., Pacific Ocean tuna). The man-made isotopes (137)Cs and (90)Sr were detectable at activities below 1 Bq/kg in the edible portions of fish from most NYS waterways, with the exception of greater activities in fish collected downstream of Brookhaven National Laboratory. Calculated effective doses resulting from eating the fish, estimated as 11-390 nSv/yr for (137)Cs and 0.3-7.9 nSv/yr for (90)Sr, are considered extremely low.

Radon measurement of natural gas using alpha scintillation cells.

Due to their sensitivity and ease of use, alpha-scintillation cells are being increasingly utilized for measurements of radon ((222)Rn) in natural gas. Laboratory studies showed an average increase of 7.3% in the measurement efficiency of alpha-scintillation cells when filled with less-dense natural gas rather than regular air. A theoretical calculation comparing the atomic weight and density of air to that of natural gas suggests a 6-7% increase in the detection efficiency when measuring radon in the cells. A correction is also applicable when the sampling location and measurement laboratory are at different elevations. These corrections to the measurement efficiency need to be considered in order to derive accurate concentrations of radon in natural gas.

Brominated flame retardant concentrations in sera from the Canadian Health Measures Survey (CHMS) from 2007 to 2009.

Pooling of surplus serum from individual samples, collected between 2007 and 2009 during Cycle 1 of the Canadian Health Measures Survey (CHMS), was performed to develop a national baseline estimate of brominated flame retardants in Canadians. Serum samples were categorized by sex and distributed by five age groups ranging from 6 to 79years. Nearly 5000 (4583) serum samples were used to form 59 composite pools. Serum pools were created to ensure a high detection frequency of these analytes in serum because low volume samples had previously resulted in non-detectable concentrations. The analytes of interest in these serum pools included 23 polybrominated diphenyl ethers (PBDEs) and three hexabromocyclododecane (HBCD) isomers (α-, ß- and γ-HBCD). PBDEs were observed in all samples tested and total PBDE concentrations ranged from 27ngg(-1) lipid to 130ngg(-1) lipid (geometric mean [GM] 46ngg(-1) lipid). ∑PBDE concentrations were significantly elevated in samples representing the 6-11year old age group (GM 65ngg(-1) lipid) relative to ages above 40years, although no difference in concentration was observed between the sexes. PBDE concentrations in Canadian sera from the general population were higher than reported in Europe and Asia, but a little lower than observed in the US. PBDE 47 was the greatest contributor to ∑PBDE concentrations and the GM concentration for this congener was 22ngg(-1) lipid. The other dominant contributors to ∑PBDE concentrations were in descending order: 153 [GM 9.4ngg(-1) lipid]>99 [GM 4.6ngg(-1) lipid]≅100 [GM 4.1ngg(-1) lipid]>209 [GM 1.1ngg(-1) lipid] and 183 [GM 0.42ngg(-1) lipid]. ∑HBCD was detected in all samples analysed, although most samples were observed at concentrations <1ngg(-1) lipid, similar to global concentrations. α-HBCD was the dominant contributor to ∑HBCD concentrations in Canadians although ß- and γ-HBCD were detected in 23% and 35% of the samples, respectively. No differences in ∑HBCD concentration were associated with age or sex. This dataset represents the first national data describing HBCD isomers and some PBDEs (e.g., 183, 209) in Canadians.

Biomonitoring of phthalate metabolites in the Canadian population through the Canadian Health Measures Survey (2007-2009).

Human exposure to phthalates occurs through multiple sources and pathways. In the Canadian Health Measures Survey 2007-2009, 11 phthalate metabolites, namely, MMP, MEP, MnBP, MBzP, MCHP, MCPP, MEHP, MEOHP, MEHHP, MnOP, and MiNP were measured in urine samples of 6-49 year old survey respondents (n=3236). The phthalate metabolites biomonitoring data from this nationally-representative Canadian survey are presented here. The metabolites MEP, MnBP, MBzP, MCPP, MEHP, MEOHP and MEHHP were detected in >90% of Canadians while MMP, MCHP, MnOP and MiNP were detected in <20% of the Canadian population. Step-wise regression analyses were carried out to identify important predictors of volumetric concentrations (µg/L) of the metabolites in the general population. Individual multiple regression models with covariates age, sex, creatinine, fasting status, and the interaction terms age×creatinine, age×sex and fasting status×creatinine were constructed for MEP, MnBP, MBzP, MCPP, MEHP, MEOHP and MEHHP. The least square geometric mean (LSGM) estimates for volumetric concentration (µg/L) of the metabolites derived from respective regression models were used to assess the patterns in the metabolite concentrations among population sub-groups. The results indicate that children had significantly higher urinary concentrations of MnBP, MBzP, MEHP, MEHHP, MEOHP and MCPP than adolescents and adults. Moreover, MEP, MBzP, MnBP and MEOHP concentrations in females were significantly higher than in males. We observed that fasting status significantly affects the concentrations of MEHP, MEHHP, MEOHP, and MCPP metabolites analyzed in this study. Moreover, our results indicate that the sampling time could affect the DEHP metabolite concentrations in the general Canadian population.

Do perfluoroalkyl substances affect metabolic function and plasma lipids?--Analysis of the 2007-2009, Canadian Health Measures Survey (CHMS) Cycle 1.

BACKGROUND: Perfluorinated compounds (PFCs) are man-made chemicals that are heat stable, non-flammable and able to repel both water and oils. Biomonitoring research shows global distribution in human, animal and aquatic environments of these chemicals. PFCs have been shown to activate the peroxisome proliferator-activated receptors which play a large role in metabolism and the regulation of energy homeostasis. Previous epidemiological research has also suggested a potential role of PFCs on lipid and glucose metabolism. OBJECTIVES: The objectives of this study were to examine the association between the levels of perfluorinated compounds perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonate (PFHxS) in plasma and metabolic function and plasma lipid levels. METHODS: Using cross-sectional data from the Canadian Health Measures Survey (Cycle 1 2007-2009) we examined the association in adults between plasma levels of PFOA, PFOS and PFHxS (n=2700) on cholesterol outcomes, metabolic syndrome and glucose homeostasis using multivariate linear and logistic regression models. RESULTS: We found some evidence of a significant association between perfluoroalkyl substances, notably PFHxS, with total cholesterol (TC), low-density lipoprotein cholesterol (LDL), total cholesterol/high density lipoprotein cholesterol ratio (TC/HDL) and non-HDL cholesterol as well as an elevated odds of high cholesterol. We found some associations with PFOA and PFOS in our unweighted models but these results did not remain significant after weighting for sampling strategy. We found no association with metabolic syndrome, or glucose homeostasis parameters. CONCLUSIONS: This study showed lower levels of PFOA and PFOS and slightly higher levels of PFHxS than other published population studies. Our results did not give significant evidence to support the association with cholesterol outcomes with PFOS and PFOA. However, we did observe several significant associations with the PFHxS and cholesterol outcomes (LDL, TC, NON-HDL, TC/HDL ratio).

PCDD/F and PCB concentrations in sera from the Canadian Health Measures Survey (CHMS) from 2007 to 2009.

In order to establish a national baseline estimate of the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in Canadians, pooling of individual human sera was performed to ensure that a high frequency of detectable concentrations of analytes would be achieved. Nearly 5000 (4583) sera samples from Cycle 1 of the Canadian Health Measures Survey (CHMS) collected between 2007 and 2009 were used to form 59 composite pools of approximately 25 mL each. Pools were categorized by sex and age with participants ranging from 6 to 79 years. The pooled samples were analysed for 17 PCDD/Fs and 36 PCB congeners, and from these data, total toxic equivalent concentrations (TEQ(2005 PCDD/F+Dioxin-like [DL]-PCB)) were estimated. The average 2,3,7,8 tetrachlorodibenzodioxin (TCDD) concentration was <1 pg g⁻¹ on a lipid extractable basis. The average total TEQ(2005 PCDD/F+DL-PCB) was 11 pg TEQ g⁻¹ lipid and average ΣPCB concentrations were about 100 ng g⁻¹ lipid. Sex did not affect the concentrations, while PCB and PCDD/F concentrations were positively correlated with age (p<0.001). It appeared in some cases that the age group 6-11 years had higher concentrations of these persistent organic pollutants (POPs) than the concentrations observed in 12-19 year olds, however, the results were not statistically significant based on pair-wise comparisons. Concentration levels and patterns observed in this study of Canadians were similar to those reported in the US and European populations.

Human biomonitoring of environmental chemicals--early results of the 2007-2009 Canadian Health Measures Survey for males and females.

Human biomonitoring is an important indicator and measure of exposure to environmental chemicals and provides information to support health protection policies and programs. Cycle 1 (2007-2009) of the Canadian Health Measures Survey (CHMS) collected and analyzed biological samples from over 5600 males and females aged 6-79 years, which established national representative blood and urine concentrations for a number of environmental chemicals including metals, organophosphate insecticide metabolites, polychlorinated biphenyls (PCBs), organochlorines (OCs), perfluorinated compounds (PFCs), bisphenol A (BPA), and cotinine. The results of CHMS Cycle 1 indicate that while some organophosphate insecticide metabolites were below limits of detection for most participants, metals, PCBs, OCs, PFCs and BPA were detected in almost all blood or urine samples. Significant differences (p<0.05) in blood concentrations between males and females were also determined for several metals (e.g., lead for males and females was 15.1 and 11.8 µg/L, respectively), PFCs (e.g., PFOS for males and females was 11.13 and 7.07 µg/L, respectively), and OCs (e.g., p,p'-DDE for males and females was 134.43 and 172.07 µg/kg lipid, respectively) and in urine concentrations for BPA (1.29 and 1.04 µg/L for males and females, respectively). Future cycles of the CHMS will permit temporal trend analysis for a number of these chemicals.

Reporting results of human biomonitoring of environmental chemicals to study participants: a comparison of approaches followed in two Canadian studies.

Biomonitoring is used increasingly as an indicator and quantitative measure of exposure; however, there is a large gap in interpreting and communicating biomonitoring results to study participants. Two separate, national biomonitoring initiatives are under way in Canada; the household recruitment-based Canadian Health Measures Survey (CHMS) and the clinic recruitment-based Maternal-Infant Research on Environmental Chemicals (MIREC) Study. The CHMS provides participants with the option to receive all their results, but this option is not provided to MIREC participants. The approach to reporting results to participants depends on the availability of reference ranges and guidelines for which tissue concentrations may be interpreted as being elevated or associated with increased health risks, how participants are recruited, unique vulnerabilities of the population, legislation governing access to personal information, and decisions of research ethics committees. It is the researchers' responsibility to present the best case for their approach and, once the decision has been made, to inform participants about access to their results through the consent process.

Lead and bisphenol A concentrations in the Canadian population.

BACKGROUND: Lead is a known toxicant that occurs naturally in the environment. Bisphenol A (BPA) is an industrial chemical used primarily in polycarbonate plastic and epoxy resins. It has been 30 years since lead exposure was measured at a national level, and it is the first time for a national assessment of BPA exposure. DATA AND METHODS: Data are from the 2007-2009 Canadian Health Measure Survey. Lead in whole blood (PbB) and urinary BPA were measured in 5319 and 5476 respondents aged 6 to 79, respectively. Geometric means (GMs) are presented by age group and sex for PbB (pg/dL), volume-based BPA (microg/L), and creatinine-standardized BPA (microg/g creatinine). Adjusted least squares geometric means (LSGMs) for PbB and BPA are presented by selected covariates. RESULTS: PbB was detected in 100% of the population, with a GM concentration of 1.34 microg/dL. Adults aged 60 to 79 and males had significantly higher GM PbB concentrations. Lower household income, being born outside Canada, living in a dwelling at least 50 years old, current or former smoking, and drinking alcohol at least once a week were associated with higher PbB concentrations. Urinary BPA was detected in 91% of the population, with a GM concentration of 1.16 microg/L (1.40 microg/g creatinine). Children aged 6 to 11 had significantly higher GM creatinine-standardized BPA concentrations than did other age groups. INTERPRETATION: Although PbB concentrations have declined dramatically since the 1970s, socio-demographic characteristics, the age of dwellings, and certain lifestyle behaviours are associated with higher levels. Given the short half-life of orally ingested BPA and the high frequency of detection, the CHMS data suggest continual widespread exposure in the Canadian population.

Emanation of radon from household granite.

Emanation of radon (222Rn) from granite used for countertops and mantels was measured with continuous and integrating radon monitors. Each of the 24 granite samples emitted a measurable amount of radon. Of the two analytical methods that utilized electret-based detectors, one measured the flux of radon from the granite surfaces, and the other one measured radon levels in a glass jar containing granite cores. Additional methods that were applied utilized alpha-scintillation cells and a continuous radon monitor. Measured radon flux from the granites ranged from 2 to 310 mBq m-2 s-1, with most granites emitting <20 mBq m-2 s-1. Emanation of radon from granites encapsulated in airtight containers produced equilibrium concentrations ranging from <0.01 to 11 Bq kg-1 when alpha-scintillation cells were used, and from <0.01 to 4.0 Bq kg-1 when the continuous radon monitor was used.

Performance of a commercial radon-in-water measurement kit.

Methods currently approved for the measurement of radon ((222)Rn) in water in New York State are liquid scintillation counting and emanation into alpha-scintillation cells. A passive system using an electret ion chamber (EIC) was evaluated as an alternative for the measurement of radon in water. Over 130 water samples from a community water supply containing 32BqL(-1) and 30 standards containing 686BqL(-1) were measured using the EIC method over 1- to 4-day exposure times. For comparison, identical samples were measured using liquid scintillation counting. Results of duplicate samples were typically within 5% for liquid scintillation counting and within 10% for the EIC. With respect to accuracy, the EIC produced results that were consistently low by 11-15%.