Urinary and serum metabolites of di-n-pentyl phthalate in rats

Di-n-pentyl phthalate (DPP) is used mainly as a plasticizer in nitrocellulose. At high doses, DPP acts as a potent testicular toxicant in rats. We administered a single oral dose of 500 mg kg⁻¹ bw of DPP to adult female Sprague-Dawley rats (N = 9) and collected 24-h urine samples 1 d before and 24- and 48-h after DPP was administered to tentatively identify DPP metabolites that could be used as exposure biomarkers. At necropsy, 48 h after dosing, we also collected serum. The metabolites were extracted from urine or serum, resolved with high performance liquid chromatography, and detected by mass spectrometry. Two DPP metabolites, phthalic acid (PA) and mono(3-carboxypropyl) phthalate (MCPP), were identified by using authentic standards, whereas mono-n-pentyl phthalate (MPP), mono(4-oxopentyl) phthalate (MOPP), mono(4-hydroxypentyl) phthalate (MHPP), mono(4-carboxybutyl) phthalate (MCBP), mono(2-carboxyethyl) phthalate (MCEP), and mono-n-pentenyl phthalate (MPeP) were identified based on their full scan mass spectrometric fragmentation pattern. The ω − 1 oxidation product, MHPP, was the predominant urinary metabolite of DPP. The median urinary concentrations (μg mL⁻¹) of the metabolites in the first 24 h urine collection after DPP administration were 993 (MHPP), 168 (MCBP), 0.2 (MCEP), 222 (MPP), 47 (MOPP), 26 (PA), 16 (MPeP), and 9 (MCPP); the concentrations of metabolites in the second 24 h urine collection after DPP administration were significantly lower than in the first collection. We identified some urinary metabolic products in the serum, but at much lower levels than in urine. Because of the similarities in metabolism of phthalates between rats and humans, based on our results and the fact that MHPP can only be formed from the metabolism of DPP, MHPP would be the most adequate DPP exposure biomarker for human exposure assessment. Nonetheless, based on the urinary levels of MHPP, our preliminary data suggest that human exposure to DPP in the United States is rather limited.     

Polycyclic musk compounds in higher trophic level aquatic organisms and humans from the United States

Polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), are used as fragrance ingredients in numerous consumer products such as cleaning agents and personal care products. Studies have reported the widespread occurrence of these musks in surface waters and fish from western European countries. Nevertheless, little is known about their accumulation in humans and wildlife in the United States. In this study, we measured concentrations of HHCB and AHTN in human adipose fat collected from New York City. Furthermore, tissues from marine mammals, water birds, and fish collected from US waters were analyzed to determine the concentrations of HHCB and AHTN. Concentrations of HHCB and AHTN in human adipose fat samples ranged from 12 to 798 and from <5 to 134 ng/g, on a lipid weight basis, respectively. A significant correlation existed between the concentrations of HHCB and AHTN in human adipose fat. Concentrations of HHCB and AHTN were not positively correlated with age or gender of the donors. HHCB was found in tissues of several wildlife species, but not in the livers of polar bear from the Alaskan Arctic. Among wildlife species analyzed, spinner and bottlenose dolphins collected from Florida coastal waters contained measurable concentrations of HHCB.     

Polybrominated diphenyl ether flame retardants in lichens and mosses from King George Island, maritime Antarctica

Lichens and mosses are considered good indicators of atmospheric pollution as they absorb contaminants directly from the air. Polybrominated diphenyl ethers (PBDEs) are man-made chemicals used as flame retardants in materials such as plastics, textiles, electronic circuitry and furnishing foam. Few studies have investigated PBDEs in the southern hemisphere including Antarctica. This paper presents the first evaluation of PBDEs in lichens (Usnea antarctica and Usnea aurantiaco-atra) and mosses (Sanionia uncinata) collected at King George Island, maritime Antarctica. PBDEs were detected at low levels in all lichen and moss samples. On average, the levels of PBDEs in mosses (818 pg g(-1) dry weight; 101 ng g(-1) lipid) were significantly higher than in lichens (168 pg g(-1) dry weight; 9.11 ng g(-1) lipid). This difference is most likely due to the differing mechanisms of PBDEs uptake from the atmosphere which are controlled by a number of chemical, environmental and plant variables. Contaminant concentrations were not statistically different at sites close to and distant from human facilities. Long-range atmospheric transport is believed to be the primary source of PBDEs to King George Island. The pattern of congeners in plants resembles those found in commercial mixtures of Penta-BDE. In addition, the presence of BDE-183 in lichens and mosses suggests that other technical formulations (e.g., Octa-BDE and Deca-BDE) have reached Antarctica. Further studies are needed to better understand the role of Antarctic vegetation as a sink for anthropogenic organic pollutants.     

Ecotoxicological evaluation of sodium fluoroacetate on aquatic organisms and investigation of the effects on two fish cell lines

Sodium monofluoroacetate (compound 1080) is one of the most potent pesticides. It is also a metabolite of many other fluorinated compounds, including anticancer agents, narcotic analgesics, pesticides or industrial chemicals. Other sources of water contamination are the atmospheric degradation of hydrofluorocarbons and hydrochlorofluorocarbons. However, there is little information available about the adverse effects of sodium fluoroacetate in aquatic organisms. Firstly, the bacterium Vibrio fischeri (decomposer), the alga Chlorella vulgaris (1st producer) and the cladoceran Daphnia magna (1st consumer) were used for the ecotoxicological evaluation of SMFA. The most sensitive models were C. vulgaris and D. magna, with a NOAEL of 0.1 and an EC50 of 0.5 mM at 72 h, respectively. According to the results after the acute exposure and due to its high biodegradation rate and low bioaccumulation potential, sodium fluoroacetate is most unlikely to produce deleterious effects to aquatic organisms. Secondly, two fish cell lines were employed to investigate the effects and mechanisms of toxicity in tissues from 2nd consumers. The hepatoma fish cell line PLHC-1 was more sensitive to SMFA than the fibroblast-like fish cell line RTG-2, being the uptake of neutral red the most sensitive bioindicator. Lysosomal function, succinate dehydrogenase and acetylcholinesterase activities were inhibited, glucose-6-phosphate dehydrogenase activity was particularly stimulated, and metallothionein and ethoxyresorufin-O-deethylase levels were not modified. Intense hydropic degeneration, macrovesicular steatosis and death mainly by necrosis but also by apoptosis were observed. Moreover, sulphydryl groups and oxidative stress could be involved in PLHC-1 cell death induced by SMFA more than changes in calcium homeostasis.     

Lead contamination in tea leaves and non-edaphic factors affecting it

Recent tests have detected high lead (Pb) concentrations in some commercial brands of tea leaves and this finding has raised concerns due to the possible health-related problems associated with Pb poisoning. In present research, we investigated the Pb contamination in tea leaves produced in Zhejiang province in China. Pb concentrations in all tea leaves sampled were below 5 mg/kg, the permissible levels given by Chinese Ministry of Agriculture, indicating that Pb contamination in this province is not excessive. We then investigated the non-edaphic factors that may potentially contribute to Pb accumulation in tea leaves. Pb concentration in tea leaves was found to be positively correlated with the industrialization level of a district (R = 0.83, the significant level at P < 0.05), and greater amounts of Pb were washed from the leaves of plants in districts with more industrial activity. This suggests that Pb accumulation in tea leaves could, in part, be attributed to industrial activity through the precipitation of atmospheric Pb. Furthermore greater amounts of Pb were washed from the leaves of plants growing near road than those growing farther away from road. This trend indicates that automobile activity was another likely contributor to Pb accumulation in tea. Pb content of green tea was also affected by the processing of the leaves in the factory. In particular the twisting and water-removal stages caused increases in Pb content in the tea product. This study suggests that non-edaphic factors also contribute to the Pb accumulation in tea.     

Aerosol ion characteristics during the Big Bend Regional Aerosol and Visibility Observational study

The ionic compositions of particulate matter with aerodynamic diameter < or = 2.5 microm (PM2.5) and size-resolved aerosol particles were measured in Big Bend National Park, Texas, during the 1999 Big Bend Regional Aerosol and Visibility Observational study. The ionic composition of PM2.5 aerosol was dominated by sulfate (SO4(2-)) and ammonium (NH4+). Daily average SO4(2-) and NH4+ concentrations were strongly correlated (R2 = 0.94). The molar ratio of NH4+ to SO4(2-) averaged 1.54, consistent with concurrent measurements of aerosol acidity. The aerosol was observed to be comprised of a submicron fine mode consisting primarily of ammoniated SO4(2-) and a coarse particle mode containing nitrate (NO3-). The NO3- appears to be primarily associated with sea salt particles where chloride has been replaced by NO3-, although formation of calcium nitrate (Ca(NO3)2) is important, too, on several days. Size-resolved aerosol composition results reveal that a size cut in particulate matter with aerodynamic diameter < or = 1 microm would have provided a much better separation of fine and coarse aerosol modes than the standard PM2.5 size cut utilized for the study. Although considerable nitric acid exists in the gas phase at Big Bend, the aerosol is sufficiently acidic and temperatures sufficiently high that even significant future reductions in PM2.5 SO4(2-) are unlikely to be offset by formation of particulate ammonium nitrate in summer or fall.     

Benzo[a]pyrene co-metabolism in the presence of plant root extracts and exudates: Implications for phytoremediation

Benzo[a]pyrene, a high molecular weight (HMW) polycyclic aromatic hydrocarbon (PAH) was removed from solution by Sphingomonas yanoikuyae JAR02 while growing on root products as a primary carbon and energy source. Plant root extracts of osage orange (Maclura pomifera), hybrid willow (Salix albaxmatsudana), or kou (Cordia subcordata), or plant root exudates of white mulberry (Morus alba) supported 15-20% benzo[a]pyrene removal over 24 h that was similar to a succinate grown culture and an unfed acetonitrile control. No differences were observed between the different root products tested. Mineralization of (14)C-7-benzo[a]pyrene by S. yanoikuyae JAR02 yielded 0.2 to 0.3% (14)CO(2) when grown with plant root products. Collectively, these observations were consistent with field observations of enhanced phytoremediation of HMW PAH and corroborated the hypothesis that co-metabolism may be a plant/microbe interaction important to rhizoremediation. However, degradation and mineralization was much less for root product-exposed cultures than salicylate-induced cultures, and suggested the rhizosphere may not be an optimal environment for HMW PAH degradation by Sphingomonas yanoikuyae JAR02.     

Backward location and travel time probabilities for a decaying contaminant in an aquifer

Backward location and travel time probabilities can be used to determine the prior position of contamination in an aquifer. These probabilities, which are related to adjoint states of concentration, can be used to improve characterization of known sources of groundwater contamination, to identify previously unknown contamination sources, and to delineate capture zones. The first contribution of this paper is to extend the adjoint model to the case of a decaying solute (first-order decay), and to describe two different interpretations of backward probabilities. The conventional interpretation accounts for the probability that a contaminant particle could decay before reaching the detection location. The other interpretation is conditioned on the fact that the detected contaminant particle actually reached the detection location, despite this possibility of decay. In either case, travel time probabilities are skewed toward earlier travel times, relative to a conservative solute. The second contribution of this paper is to verify the load term for a monitoring well observation. We provide examples using one-dimensional models and hypothetical aquifers. We employ an infinite domain in order to verify the monitoring well load. This new but simple one-dimensional adjoint solution can also be used to verify higher-dimensional numerical models of backward location and travel time probabilities. We employ a semi-infinite domain to illustrate the effect of decay on backward models of pumping well probabilistic capture zones. Decay causes the capture zones to fall closer to the well.     

Environmental impact of a new hazardous waste incinerator in Catalonia,Spain: PCDD/PCDF levels in herbage samples

In April 1996 and 1998, the concentrations of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in 40 herbage samples collected in the neighborhood of a hazardous waste incinerator (HWI) under construction in Constanti (Catalonia, Spain). In April 2000, 20 months after the HWI began operating, herbage samples were again collected at the same sampling points in which samples had been taken in the previous surveys. PCDD/F concentrations ranged between 0.13 and 0.65 ng I-TEQ/kg (dry matter), with a median and mean values of 0.29 and 0.32 ng I-TEQ/kg (dry matter), respectively. The results were compared with those obtained in the 1996 (median, 0.53 ng I-TEQ/kg; mean, 0.61 ng I-TEQ/kg) and the 1998 (median, 0.23 ng I-TEQ/kg; mean, 0.31 ng I-TEQ/kg) surveys. While in the period 1996-1998 a significant decrease (49%, P < 0.001) in the mean PCDD/F levels was noted, in the period 1998-2000 an increase of 3% (P > 0.05) was found in the concentrations of PCDD/Fs. The analysis of the results suggests two potential hypotheses: either the emissions of PCDD/Fs from the HWI are not negligible, or the current PCDD/F emissions from other sources near the HWI remained at similar levels to those reached in 1998. Anyhow, an exhaustive evaluation of the present data shows an absence of notable PCDD/F contamination by the HWI in the area under its direct influence. It seems also probable that the decline in the atmospheric levels of PCDD/Fs due other emission sources of PCDD/Fs in this area is currently stopped.