The occurrence and fate of 14 triester organophosphate flame retardants (OPFRs) and plasticizers and their two diester metabolites were investigated in a wastewater treatment plant (WWTP) in the Albany area of New York State. All target OPFRs were found in wastewater, with average concentrations that ranged from 20.1 ng/L for tris(methylphenyl) phosphate (TMPP) to 30 100 ng/L for tris(2-butoxyethyl)phosphate (TBOEP) in influents and from 7.68 ng/L for TMPP to 12 600 ng/L for TBOEP in final effluents. TBOEP was the dominant compound in influents (max: 69 500 ng/L) followed in decreasing order by tris(1-chloro-2-propyl)phosphate (TCIPP; max: 14 500 ng/L), bis(1,3-dichloro-2-propyl)phosphate (BDCIPP; max: 4550 ng/L), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP; max: 3150 ng/L) and tris(2-chloroethyl)phosphate (TCEP; max: 8450 ng/L). The fraction of TMPP sorbed to suspended particulate matter (SPM) was 56.4% of the total mass in wastewater, which was the highest among the target chemicals analyzed. The average concentrations of OPFRs in sludge were between 4.14 ng/g dw for tripropyl phosphate (TPP) and 7290 ng/g dw for TBOEP; for ash, they were between 2.17 ng/g dw for TMPP and 427 ng/g dw for triphenyl phosphate (TPhP). The mass loadings of OPFRs into the WWTP ranged from 0.02 mg/day/person for TPP to 28.7 mg/day/person for TBOEP, whereas the emission from the WWTP ranged from 0.01 mg/day/person for 2-ethylhexyl diphenyl phosphate (EHDPP) to 5.12 mg/day/person for TCIPP. The removal efficiencies for OPFRs were slightly above 60% for TMPP, TBOEP, and tris(2-ethylhexyl)phosphate (TEHP) whereas those for other OPFRs were <40% (TPhP and BDCIPP) to negative values, suggesting incomplete removal in WWTPs.
Benzothiazole and its derivatives (BTs) are high production volume chemicals that have been used for several decades in a large number of industrial and consumer products, including vulcanization accelerators, corrosion inhibitors, fungicides, herbicides, algicides, and ultraviolet (UV) light stabilizers. Several benzothiazole derivatives are used commercially, and widespread use of these chemicals has led to ubiquitous occurrence in diverse environmental compartments. BTs have been reported to be dermal sensitizers, respiratory tract irritants, endocrine disruptors, carcinogens, and genotoxicants. This article reviews occurrence and fate of a select group of BTs in the environment, as well as human exposure and toxicity. BTs have frequently been found in various environmental matrices at concentrations ranging from sub-ng/L (surface water) to several tens of μg/g (indoor dust). The use of BTs in a number of consumer products, especially in rubber products, has resulted in widespread human exposure. BTs undergo chemical, biological, and photolytic degradation in the environment, creating several transformation products. Of these, 2-thiocyanomethylthio-benzothiazole (2-SCNMeS-BTH) has been shown to be the most toxic. Epidemiological studies have shown excess risks of cancers, including bladder cancer, lung cancer, and leukemia, among rubber factory workers, particularly those exposed to 2-mercapto-benzothiazole (2-SH-BTH). Human exposure to BTs continues to be a concern.
The occurrence and profiles of 14 triester organophosphate flame retardants (OPFRs) and plasticizers were investigated in surface water, tap water, rainwater, and seawater collected from New York State. In total, 150 samples collected from rivers ( n = 35), lakes ( n = 39), tap water ( n = 58), precipitation/rainwater ( n = 15), and seawater ( n = 3) were analyzed for 14 organophosphate esters (OPEs). An additional nine Hudson River water samples were collected periodically to delineate seasonal trends in OPE levels. The total concentrations of OPEs were found at part-per-trillion ranges, with average concentrations that ranged from 0.01 ng/L for tripropyl phosphate (TPP) in river water to 689 ng/L for tris(2-butoxyethyl)phosphate (TBOEP) in lake water. Tris(1-chloro-2-propyl)phosphate (TCIPP) was the most abundant compound among the investigated OPEs in all types of water. The concentrations of OPEs in river-, lake-, and rainwater were similar but >3 times higher than those found in tap water. Chlorinated alkyl OPFRs accounted for a major proportion of total concentrations. TCIPP, TBOEP, and triethyl phosphate (TEP) were found in >90% of the samples analyzed. Wet deposition fluxes for 14 OPFRs were estimated, on the basis of the concentrations measured in rainwater in Albany, New York, and the values were between 440 and 5250 ng/m. Among several surface water bodies analyzed, samples from the Hudson River and Onondaga Lake contained elevated concentrations of OPEs. Estimated daily intake of OPEs via the ingestion of drinking water was up to 9.65 ng/kg body weight/day.
In
the 2000s, nail polish manufacturers started promoting “3-Free”
products, phasing out three widely publicized toxic chemicals: toluene,
formaldehyde, and dibutyl phthalate (DnBP). However, DnBP was
sometimes replaced by another endocrine-disrupting plasticizer,
triphenyl phosphate (TPHP). Many new “n-Free”
labels have since appeared, without any standardization on which n chemicals are excluded. This study aimed to compare measured
plasticizer content against nail polish labels. First, we summarized
definitions of labels. Then, we measured 12 phthalate and 10 organophosphate
plasticizers in 40 nail polishes from 12 brands selected for popularity
and label variety. We found labels ranging from 3- to 13-Free; 10-Free
was the most inconsistently defined (six definitions). Our samples
contained TPHP and bis(2-ethylhexyl) phthalate (DEHP) at up to 7940
and 331 μg/g, respectively. The 5- to 13-Free samples had lower
TPHP levels than unlabeled or 3-Free samples (median <0.002 vs
3730 μg/g, p < 0.001). The samples that
did not contain TPHP had higher DEHP levels (median 68.5 vs 1.51 μg/g, p < 0.05). We measured plasticizers above 100 μg/g
in five brands that did not disclose them and in two that excluded
them in labels. This study highlights inconsistencies in nail polish
labels and identifies TPHP and DEHP as ingredient substitutes for
DnBP.
Background
Titanium dioxide (TiO
2
) nanoparticles are among the most manufactured nanomaterials in the industry, and are used in food products, toothpastes, cosmetics and paints. Pregnant women as well as their conceptuses may be exposed to TiO
2
nanoparticles; however, the potential effects of these nanoparticles during pregnancy are controversial, and their internal distribution has not been investigated. Therefore, in this study, we investigated the potential effects of oral exposure to TiO
2
nanoparticles and their distribution during pregnancy. TiO
2
nanoparticles were orally administered to pregnant Sprague-Dawley rats (12 females per group) from gestation days (GDs) 6 to 19 at dosage levels of 0, 100, 300 and 1000 mg/kg/day, and then cesarean sections were conducted on GD 20.
Results
In the maternal and embryo-fetal examinations, there were no marked toxicities in terms of general clinical signs, body weight, food consumption, organ weights, macroscopic findings, cesarean section parameters and fetal morphological examinations. In the distribution analysis, titanium contents were increased in the maternal liver, maternal brain and placenta after exposure to high doses of TiO
2
nanoparticles.
Conclusion
Oral exposure to TiO
2
during pregnancy increased the titanium concentrations in the maternal liver, maternal brain and placenta, but these levels did not induce marked toxicities in maternal animals or affect embryo-fetal development. These results could be used to evaluate the human risk assessment of TiO
2
nanoparticle oral exposure during pregnancy, and additional comprehensive toxicity studies are deemed necessary considering the possibility of complex exposure scenarios and the various sizes of TiO
2
nanoparticles.
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