Heavy metals in human urine, foods and drinking water from an e-waste dismantling area: Identification of exposure sources and metal-induced health risk.

Electronic waste or e-waste dismantling activities are known to release metals. However, the human exposure pathways of metals, and their association with oxidative stress in e-waste dismantling areas (EDAs) remain unclear. In this study, our results revealed elevated geometric mean concentrations in vegetables (Cd 0.096 and Pb 0.35 µg/g fw), rice (Cd 0.15, Pb 0.20, and 12.3 µg/g fw), hen eggs (Cd 0.006 and Pb 0.071 µg/g fw), and human urine (Cd 2.12, Pb 4.98, Cu 22.2, and Sb 0.20 ng/mL). Our calculations indicate that rice consumption source accounted for the overwhelming proportion of daily intakes (DIs) of Cd (61-64%), Cu (85-89%), and Zn (75-80%) in children and adults living in EDA; vegetables were the primary contributors to the DIs of Cd (30-32%); and rice (20-29%), vegetables (28-38%), and dust ingestion (26-45%) were all important exposure sources of Pb. Risk assessment predicted that DIs of Cd, Pb, Cu, and Zn via food consumption poses health risks to local residents of EDAs, and the urinary concentrations of analyzed metals were significantly (Pearson correlation coefficient: r = 0.324-0.710; p < 0.01) associated with elevated 8-OHdG, a biomarker of oxidative stress in humans.

Within-person variability of urinary neonicotinoids and their metabolites and recommendation for sampling strategy.

Humans are exposed to neonicotinoid insecticides (NEOs) from various routes. Urine has been widely used to characterize the internal exposure levels of NEOs in humans. However, variable sampling methods can result in highly variable measurements of NEOs, potentially leading to misunderstanding of human exposure. In this study, we collected the first morning voids urine (FMVU), spot urine (SU), and 24 h urine (24hU) samples from 8 healthy adults during 7 consecutive days. The concentration, variability, and reproducibility of six parent NEOs (p-NEOs) and three NEOs metabolites (m-NEOs) were measured. Over 79 % of the urine samples had detectable levels of NEOs. Dinotefuran (DIN) and olefin-imidacloprid (of-IMI) were excreted in the highest concentration of p-NEO and m-NEO, respectively. All of the p-NEOs except thiacloprid (THD) and of-IMI were recommended as biomarkers for biomonitoring studies. The coefficient of variation (CV) and intraclass correlation coefficient (ICC) were used to evaluate the temporal variability and reproducibility of urinary NEOs in SU, FMVU and 24hU, respectively. We observed low ICCs ranging from 0.016 to 0.39 for NEOs regardless of the sample types. However, the higher CV and lower ICC values observed in SU samples suggested lower reproducibility compared to FMVU and 24hU samples. Significant correlations of several NEOs between FMVU and 24hU were also observed in the current study. Considering the comparable concentrations and similarity between FMVU and 24hU, our study proposed possible biomarkers and indicated that the potential for FMVU samples to estimate adequately an individual's exposure to NEOs. Therefore, we suggested FMVU as a sampling strategy in future human biomonitoring studies, while multiple samples were recommended to detect exposure over time intervals of weeks or months.

A nationwide survey of urinary concentrations of neonicotinoid insecticides in China.

Neonicotinoid insecticides (NEOs) are emerging pesticides of concern due to their potential toxicity to non-target species (e.g., bees, fish and birds). China is an important producer and user of NEOs in the world. Studies on human exposure to NEOs in China are very limited. In this study, urinary levels of six NEOs, namely acetamiprid (ACE), clothianidin (CLO), dinotefuran (DIN), imidacloprid (IMI), thiacloprid (THD), and thiamethoxam (THM) were determined in 324 individuals from 13 cities in China. Across all sampling locations, total NEO concentrations (ΣNEOs; sum of six NEOs) were dominated by CLO (median: 0.24 ng/mL), IMI (0.21 ng/mL), THM (0.15 ng/mL) and DIN (0.14 ng/mL) collectively accounting for 98% of the concentrations. Urinary concentrations of each NEO varied depending on the sampling location with the median values ranged from 0.057 to 1.2 ng/mL for CLO, from 0.036 to 0.83 ng/mL for DIN, from 0.069 to 3.2 ng/mL for IMI, and from 0.062 to 0.45 ng/mL for THM. Sex-related differences in IMI, ACE and ΣNEOs concentrations were observed with males presenting significantly higher urinary levels than did females. All six NEOs were significantly positively correlated (r = 0.135 to 0.661, p < 0.05) with each other, suggesting that the exposure sources of NEOs are common or related. On the basis of urinary IMI levels, we calculated the median daily intake (DI; mean and range) of IMI to be 1.6 (4.1, <0.02-55) µg/day, or 0.034 (0.11, <0.0003-2.1) µg/kg bw/day. To our knowledge, this is the first study to document the ubiquitous occurrence of and human exposure to NEOs in China.

Urinary benzophenone-type UV filters in people living in South China: rural versus urban areas.

Benzophenone (BP)-type UV filters are widely used in sunscreen products to protect human skin from UV radiation. However, only a few studies have been conducted to determine the level of human exposure to BPs in rural areas of China. In this study, we evaluated the exposure levels of people living in three villages and a city in South China to five major BPs (BP-1, BP-2, BP-3, BP-8, and 4-OH-BP). The detection rates of BP-1, BP-3, and 4-OH-BP were 66%, 72%, and 75%, respectively, in rural areas and 85%, 75%, and 80%, correspondingly, in urban areas. BP-2 and BP-8 were rarely detected. The results indicated that people living in South China are extensively exposed to BPs, regardless of sampling sites (rural and urban areas). The observed concentrations of BP-1 (urban vs. rural = 1.04 ng mL-1vs. 0.21 ng mL-1) and BP-3 (0.37 ng mL-1vs. 0.16 ng mL-1) were significantly (one-way ANOVA, p < 0.01) lower in the rural areas than in the urban areas. BP-1 (59%) based on composition profile analysis was the dominant BP derivative in urine samples of urban residents, whereas 4-OH-BP (36%) was the most prevalent BP in rural areas. In the rural areas, significant positive correlations between urinary BP-1 and BP-3 (r = 0.529, p < 0.01) and between urinary BP-1 and 4-OH-BP (r = 0.323, p < 0.05) concentrations were obtained; in the urban areas, we only observed a clear correlation (p < 0.01) between BP-1 and 4-OH-BP. The different composition profiles and associations among urinary BPs indicated that exposure sources of BPs might be different between rural and urban areas. The distribution profiles of BP-1 and its parent compound (i.e., BP-3) in urine decreased with the age of adults (r = -0.410, p < 0.01) in the rural areas.

Urinary metabolites of organophosphate flame retardants in China: Health risk from tris(2-chloroethyl) phosphate (TCEP) exposure.

Organophosphate esters (OPs) are substitutes for polybrominated diphenyl ether (PBDE) flame retardants. China is the largest producer of OPs globally, with the production rate increasing at 15% annually. Since some OPs are neurodevelopmental and/or carcinogenic toxicants, human exposure is a concern. In this study, concentrations of eight OP metabolites (mOPs) were measured in human urine samples collected from 13 cities located in Northern, Eastern, Southern, and Southwestern China. All target mOPs were frequently detected with detection rates of 50% to 100%, indicating widespread human exposure to OPs. Bis(2-chloroethyl) phosphate (BCEP; median: 0.68 ng/mL), bis(1-chloro-2-propyl) phosphate (BCIPP; 0.30 ng/mL), diphenyl phosphate (DPHP; 0.30 ng/mL), and dibutyl phosphate (DBP; 0.29 ng/mL) were the dominant mOPs across all participants. Regional differences in concentrations (ΣmOPs varied from 0.86 to 3.7 ng/mL) and composition profiles (contribution of chlorinated mOPs to ΣmOPs varied from 35% to 95%) of mOPs were observed within China. In comparison to the concentrations reported worldwide, urinary DPHP and bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) levels in China were lower, whereas BCEP and DBP levels were comparable or higher. The total daily intake (TDI) of tris(2-chloroethyl) phosphate (TCEP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP) were estimated from daily urine excretion rate and the fraction of OP metabolized in human liver microsomes (TDIHLM) or S9 fraction (TDIS9). The intake estimates showed that Chinese residents were exposed to TCEP from 96.9 to 46,700 (or 52.2 to 25,200) ng/kg bw/day. Depending on the reference dose, we found that approximately 5% of the individuals exceeded the limit (i.e., 2200 ng/kg bw/day) for TCEP intake. To our knowledge, this is the first nationwide baseline survey to determine urinary levels of mOPs in Chinese residents.