Nontarget Identification of Novel Organophosphorus Flame Retardants and Plasticizers in Indoor Air and Dust from Multiple Microenvironments in China.

The indoor environment is a typical source for organophosphorus flame retardants and plasticizers (OPFRs), yet the source characteristics of OPFRs in different microenvironments remain less clear. This study collected 109 indoor air samples and 34 paired indoor dust samples from 4 typical microenvironments within a university in Tianjin, China, including the dormitory, office, library, and information center. 29 target OPFRs were analyzed, and novel organophosphorus compounds (NOPs) were identified by fragment-based nontarget analysis. Target OPFRs exhibited the highest air and dust concentrations of 46.2-234 ng/m3 and 20.4-76.0 µg/g, respectively, in the information center, where chlorinated OPFRs were dominant. Triphenyl phosphate (TPHP) was the primary OPFR in office air, while tris(2-chloroethyl) phosphate dominated in the dust. TPHP was predominant in the library. Triethyl phosphate (TEP) was ubiquitous in the dormitory, and tris(2-butoxyethyl) phosphate was particularly high in the dust. 9 of 25 NOPs were identified for the first time, mainly from the information center and office, such as bis(chloropropyl) 2,3-dichloropropyl phosphate. Diphenyl phosphinic acid, two hydroxylated and methylated metabolites of tris(2,4-ditert-butylphenyl) phosphite (AO168), and a dimer phosphate were newly reported in the indoor environment. NOPs were widely associated with target OPFRs, and their human exposure risk and environmental behaviors warrant further study.

In vitro lung and gastrointestinal bioaccessibility of potentially toxic metals in Pb-contaminated alkaline urban soil: The role of particle size fractions.

Potentially toxic metals (PTMs), associated with different size particles in soil, may play an important role in adverse health effect and risk for human. The objective is to evaluate the lung and gastrointestinal bioaccessibility and risk of PTMs in Pb-contaminated alkaline urban soil depending on the particle size fractions. The size fractions of 50-250 µm, 5-50 µm, 1-5 µm, <1 µm in Pb-contaminated alkaline urban soil from Baoji Heavy Industrial Base City, NW China, were screened by Sequential Wet Sieving Separation Procedure (SWSSP) based on Stokes' Law. The concentrations of 9 potentially toxic metals (As, Ba, Co, Cr, Cu, Mn, Ni, Pb and Zn) in each particle size fractions were characterized by ICP-OES and ICP-MS, and the in vitro bioaccessibility dependent of size fractions were evaluated by the simulation fluids of Artificial Lysosomal Fluid (ALF) and Gamble for lung, PBET, SBET, IVG, SBRC, UBM for gastric and intestinal, respectively. Health risks were assessed considering simulated external exposure using intestinal and lung bioaccessibility. The lung and gastrointestinal bioaccessibility and exposure risks of PTMs in fine particle size (i.e. <1 µm) was higher than larger particle size fractions (i.e. 50-250 µm, 5-50 µm, 1-5 µm), however, some different variations of bioaccessibility observed the simulation fluids and time dependent. In case of single PTMs, the lung bioaccessibilities of PTMs in ALF were higher than those in Gamble fluids, most prominent in Co, Cu, Mn and Zn, while the gastrointestinal [G + I] bioaccessibility of PTMs was less than those in gastric [G], like Cu, Mn, Pb and Zn mostly. The non-carcinogenic risks of these PTMs to children via inhalation were acceptable and higher than those of adults, but reverse for carcinogenic risk. Comparatively, the non-carcinogenic and carcinogenic risks of PTMs via ingestion pathway were both higher than those for adults. Although the risks from ingestion were in acceptable range, the total carcinogenic risks for children were more than 10-4, which would bring carcinogenic risks and should be paid attention to. It was noted that the toxic metal, Co in all size fractions was the most important contributor for noncarcinogenic risks and Cr mostly for carcinogenic risks via inhalation pathway for adults and children in local areas. However, Pb was the most important contributor for noncarcinogenic risk both for adults and children via ingestion pathway relative to Co and Cr for carcinogenic risks through hand-to-mouth ingestion. Those observations demonstrated the important role that the smaller particle fractionations in Pb-contaminated alkaline soil played in both bioaccessibility and the refinement of human health-risk assessments for the inhalation and ingestion pathway.

Exposure risks of lead and other metals to humans: A consideration of specific size fraction and methodology.

Particle size is a critical influencing factor in assessing human exposure risk as fine particles are generally more hazardous than larger coarse particles. However, how particle composition influences human health risk is only poorly understood as different studies have different utilised different definitions and as a consequence there is no consensus. Here, with a new methodology taking insights of each size fraction load (%GSFload), metal bioaccessibility, we classify which specific particle size can reliably estimate the human exposure risk of lead and other metals. We then validate these by correlating the metals in each size fraction with those in human blood, hair, crop grain and different anthropogenic sources. Although increasing health risks are linked to metal concentration these increase as particle size decrease, the adjusted-risk for each size fraction differs when %GSFload is introduced to the risk assessment program. When using a single size fraction (250-50 µm, 50-5 µm, 5-1 µm, and < 1 µm) for comparison, the risk may be either over- or under-estimated. However, by considering bulk and adjusting the risk, it would be possible to obtain results that are closer to the real scenarios, which have been validated through human responses and evidence from crops. Fine particle size fractions (< 5 µm) bearing the mineral crystalline or aggregates (CaCO3, Fe3O4, Fe2O3, CaHPO4, Pb5(PO4)3Cl) alter the accumulation, chemical speciation, and fate of metals in soil/dust/sediment from the different sources. Loaded lead in the size fraction of < 50 µm has a significantly higher positive association with the risk-receptor biomarkers (BLLs, Hair Pb, Corn Pb, and Crop Pb) than other size fractions (bulk and 50-250 µm). Thus, we conclude that the < 50 µm fraction would be likely to be recommended as a reliable fraction to include in a risk assessment program. This methodology acts as a valuable instrument for future research undertakings, highlighting the importance of choosing suitable size fractions and attaining improved accuracy in risk assessment results that can be effectively compared.

Dysregulation of steroid metabolome in follicular fluid links phthalate exposure to diminished ovarian reserve of childbearing-age women.

The widespread use of phthalates (PAEs) has drawn increasing attention due to their endocrine disruption and reproductive toxicity, while the steroid metabolome is essential for follicular development. However, the mechanism by which PAE exposure affects ovarian reserve through the steroid metabolome remains unclear. This study recruited 264 childbearing-age women in Tianjin (China) from April 2019 to August 2020 in a cross-sectional design. Target metabolome analysis of 16 steroids was performed in follicular fluid (FF) to compare diminished ovarian reserve (DOR) against normal ovarian reserve (NOR) women and differential steroids were identified using binary logistic analyses. Further analysis of eleven PAE metabolites (mPAEs) in FF was conducted, and the retrieved oocyte number (RON) representing ovarian reserve was counted. Multiple linear regression and quantile-based g-computation (qgcomp) models were used to associate individual mPAEs and mPAE mixture with the DOR-related differential steroids in FF. Mediation analysis was used to discuss the mediating effect of DOR-related steroids on the association between mPAEs and RON. Androstenedione (A4), corticosterone (CORT), cortisol (COR) and cortisone were significantly down-regulated in FF from women with DOR. Nine mPAEs with detection frequencies greater than 60% and median concentrations of 0.02-4.86 ng/mL were incorporated into statistical models. Negative associations with COR and CORT were found for mono-ethyl phthalate (mEP), mono-(2-ethyl-5-oxohexyl) phthalate (mEOHP), and mono-2-ethylhexyl phthalate (mEHP). A positive association with cortisone was found for mEOHP, mEHP, monobutyl phthalate (mBP), and mono (2-isobutyl) phthalate (miBP). The qgcomp and mediation analyses revealed that mEP and mEOHP not only significantly contributed to the decline of COR and CORT in the mixed exposure but also indirectly reduced RON through the mediating effects of COR and CORT. In conclusion, PAE exposure may decrease ovarian reserve by downregulating COR and CORT.

Comprehensive Urumqi screening for potentially toxic metals in soil-dust-plant total environment and evaluation of children's (0-6 years) risk-based blood lead levels prediction.

Environmental contaminations by potentially toxic metals (PTMs) are associated with energy exploitation and present a significant problem in urban areas due to their impacts on human health. The PTMs status in Urumqi total environment inevitably impacted by extensive development of coal and oil industries has been lack of understanding comprehensively. A series of PTMs (As, Ba, Ce, Co, Cr, Cu, Ga, La, Mn, Ni, Pb, Rb, Sr, Th, U, V, Y, Zn, Zr) in the soil-dust-plant (foliage of Ulmus pumila L.) system of Urumqi (NW China) were screened by XRF and ICPMS. Multivariate statistics, risk models, GIS-based geostatistics, Positive Matrix Factorization (PMF) receptor modelling and blood lead levels of 0-6 aged children evaluated by IEUBK model are used to determine the priority pollutants, sources and health effects of the investigated elements. The spatial distribution of PTMs in soil-dust-plant system significantly coincides with coal combustion, traffic emission, and industrial activity. Although all PTM toxicants in soil, dust and tree foliage show some effects, the priority contaminants are observed for Cu, Pb and Zn as single element. The total carcinogenic and non-carcinogenic risks from PTMs are beyond the tolerance range of 0-6 year's old children, and the dust (TCR = 1.07E-04) PTMs pose approximatively equivalent carcinogenic risk to soil PTMs (TCT = 1.09E-04). The predicted BLLs (75-83 µ g·L-1) of 1-2 years children are most strongly influenced by Pb in soil and dust, and therefore more attention should be focused on sources of Pb to support the primary health care of the toddlers in Urumqi.

Potentially toxic metals and the risk to children's health in a coal mining city: An investigation of soil and dust levels, bioaccessibility and blood lead levels.

Coal is a primary energy source in the world. Potentially toxic metals (PTMs) emission from coal mining and combustion are posing a serious public health concern. In order to quantify and evaluate the effect of PTMs on children's health, the concentrations of 12 PTMs (As, Co, Cr, Cu, Mn, Ni, Pb, Sr, Zn, Ca, Fe, and Mg) bound in urban soil and street dust are determined and blood lead levels of these PTMs in 229 children (0-6 years old) are collected from the coal mining city of Yulin, China. In vitro pulmonary bioaccessibilities of PTMs are evaluated by artificial lysosomal fluid and Gamble's solution, and gastrointestinal bioaccessibilities by the unified BAGRE method (UBM); correlations between chemical speciation of PTMs and their bioaccessibility are examined, and children's (0-6 years old) health risks are systematically studied. Similar distribution levels of PTMs are found in soils and dusts, with the most polluted metals being Co, Sr, Ca and Pb. All PTMs (except Cr, Fe) are from the considerable artificial lysosomal fluid extraction both in soil and dust, while Ca and Co are favorably extracted in gastro and intestinal phases than others. Significant correlations are observed between the bioaccessibilities (lung and gastrointestinal) and Fe/Mn hydroxide-bound and carbonate-bound phases, which are key factors influencing and determining PTMs' bioaccessibility. Blood lead levels for children (0-6 years old) are 27.47 (21.65, 33.30) for 0-1 year olds, 32.29 (26.39, 38.19) for 1-2 year olds, 36.99 (28.16, 45.81) for 2-3 year olds, 30.79 (22.56, 39.01) for 3-4 year olds, 27.12 (17.31, 36.93) for 4-5 year olds, 34.59 (24.22, 44.97) for 5-6 year olds and 37.83 (24.15, 51.51) µg/L for 6-7 year olds, respectively, with 3.93%, 3.49%, 4.80%, 2.62%, 1.31%, 1.75% and 1.31% exceeding 50 µg/L, respectively. This indicates that the blood lead levels elevate for 1-2 year and 5-6 year old groups, which should be paid more attention. Although the non-carcinogenic and carcinogenic risks of most PTMs are under the acceptable level, the higher carcinogenic risk of Ni and non-carcinogenic risk of Pb should be monitored continuously. We suggest that further actions will be taken to reduce PTMs exposure for children through sustainable clean and ecological energy technology for coal mining, especially for those infants of 1-2 years old.

Spatial Distributions, Sources, Potential Risks of Multi-Trace Metal/Metalloids in Street Dusts from Barbican Downtown Embracing by Xi'an Ancient City Wall (NW, China).

A total of 116 dust samples in downtown within the city wall were collected, and the spatial occurrence, source and health risk status of 19 trace metal/metalloids bound in street dusts (SDs) were systematically investigated. Geochemical maps, associations, risk models and indices were calculated to define levels of distribution, possible natural or anthropogenic sources, ecological and human health risks. It was found that the wide variations of these 19 trace metals would be observed in spatial maps, which indicated strongly anthropogenic activities inputs. Compared to the calculations of the potential ecological risk index of toxic trace metals, Pb (Eri = 20.32) ranked at the level of considerable ecological risk. The non-carcinogenic and carcinogenic risk from most trace metals exposed to children and adults were no significant health risks, except for the non-carcinogenic risk of Cr and As to children, and the carcinogenic risk of Cr to adults. The unacceptable risk locations were observed at traffic conjunctions, which should be given attention. The source apportionment results indicated that the trace metals/metalloids Co, Ga, Nb, As, Ni, and Y, coupled with main elements Al, K, Mg, Ca and Si, would possibly originate from "Soil Re-suspension", whereas Fe, Cu, Rb, La, Ba, Mn, Ti, Ce and Zr were possibly derived from "Brake Wear". As regards the Na, no valid assumption was formulated about the presence of this element in brake wear, while Cr, Sr, Zn were possibly associated with "Tire Wear". Comparatively, V would be suggested as a representative source of fuel consumption, and Pb could possibly belong to "Traffic Pigment". It was noted that the barbican city, surrounded by the Xi'an Ancient City Wall at 12 m high, would trap the trace metal emissions, and consequently increase the health risk for local residents.