Polycyclic aromatic hydrocarbons in breast milk of nursing mothers: Correlates with household fuel and cooking methods used in Uganda, East Africa.

Maternal breast milk, which is a complete food for the infant's growth, development, and health, contains fats and lipids making it susceptible to accumulation of lipophilic compounds like polycyclic aromatic hydrocarbons (PAHs). This study aimed at analyzing correlates of measured levels of PAHs in breast milk of nursing mothers to frequently used household fuels and cooking methods in Uganda, and estimate the potential health risks of PAHs to infants through breastfeeding. Sixty breast milk samples were collected from healthy and non-smoking mothers who had lived in Kampala capital city (urban area) and Nakaseke district (rural area) for at least five years. Sample extracts were analyzed for PAHs using a gas chromatograph coupled with a triple quadrupole mass spectrometer. ∑13PAHs in samples from Kampala ranged from 3.44 to 696 ng/g lw while those from Nakaseke ranged from 0.84 to 87.9 ng/g lw. PAHs with 2-3 rings were more abundant in the samples than PAHs with 4-6 rings. At least 33 % of the variance in the levels of ∑13PAHs in the breast milk samples was attributable to the fuel type and cooking methods used. Nursing mothers who used charcoal for cooking accumulated higher levels of ∑13PAHs in their breast milk samples compared to those who used firewood. Levels of ∑13PAHs in breast milk of mothers increased depending on the cooking methods used in the order; boiling< grilling< deep-frying. In all samples, hazard quotients for PAHs were <1 and estimated incremental cancer risks were all between 10-6 and 10-4, indicating that the health risks to infants due to the ingestion of PAHs in breast milk was tolerable. Further studies with large datasets on PAHs and their derivatives and, larger samples sizes are needed to confirm these findings.

Polycyclic aromatic hydrocarbons and trace metal contamination of coastal sediment and biota from Togo.

The state of contamination of tropical environments, particularly in Africa, remains a relatively under explored subject. Here, we determined polycyclic aromatic hydrocarbon (PAH) and trace metal concentrations in coastal sediment and biota samples (fish and mussels) from Togo (West Africa). In the sediments, the ∑21 PAH concentrations ranged from <4 ng g(-1) to 257 ng g(-1), averaging 92 ng g(-1). Concentration ratios of low molecular weight PAHs (2-3 rings) versus high molecular weight PAHs (≥4 rings) were always lower than 1 (ranging from 0.08 to 0.46) indicating that high molecular weight PAHs were dominant in all sediment samples, and that PAHs originated mainly from anthropogenic combustion activities. The sediments were also analyzed for major elements and a total of 15 trace metals, which were found in elevated concentrations. The calculated enrichment factor (EF) values relative to the Earth's crust show that the contamination is extremely severe for Cd (EF = 191), severe for Cr (EF = 18) and U (EF = 17.8), moderately severe for Zr (EF = 8.8), for Ni (EF = 6.8), Sr (EF = 5.9) and Ba (EF = 5.4), and moderate for V (EF = 3.6) and Zn (EF = 3.4). Sediments sampled in areas affected by the dumping of phosphorite mine tailings showed particularly high concentrations of trace metals. Overall, concentrations of both PAHs and trace metals in sediment tend to increase from the coastline to the open sea (2 km offshore). This is attributable to the increasingly finer texture of coastal sediment found offshore, which has a terrigenous origin and appears loaded with various contaminants through adsorption processes. Such high loads of trace metals were also found in the biota (fish and mussels). The ratio of measured trace metal concentrations in biota to threshold limits set by the World Health Organization herein defined as relative health factor (RHF) was high. Average RHF values in fish were highest for Se (470), As (250), Ag (97), Ni (78), Mn (63), Fe (53), Pb (36), Cd (10), and Cr (7) while lowest for Cu (0.08) and Zn (0.03). Cd and Al did not bioaccumulate in the analyzed fish species. In mussels, the RHF values were highest for Fe (9,108), As (295), Pb (276), Se (273), Mn (186), Ni (71), Ag (70), Cd (14), and Cu (4).

Global distribution of oxygenated polycyclic aromatic hydrocarbons in mineral topsoils.

Hazardous oxygenated polycyclic aromatic hydrocarbons (OPAHs) originate from combustion (primary sources) or postemission conversion of polycyclic aromatic hydrocarbons (PAHs) (secondary sources). We evaluated the global distribution of up to 15 OPAHs in 195 mineral topsoils from 33 study sites (covering 52° N-47° S, 71° W-118 °E) to identify indications of primary or secondary sources of OPAHs. The sums of the (frequently measured 7 and 15) OPAH concentrations correlated with those of the Σ16EPA-PAHs. The relationship of the Σ16EPA-PAH concentrations with the Σ7OPAH/Σ16EPA-PAH concentration ratios (a measure of the variable OPAH sources) could be described by a power function with a negative exponent <1, leveling off at a Σ16EPA-PAH concentration of approximately 400 ng g-1 . We suggest that below this value, secondary sources contributed more to the OPAH burden in soil than above this value, where primary sources dominated the OPAH mixture. This was supported by a negative correlation of the Σ16EPA-PAH concentrations with the contribution of the more readily biologically produced highly polar OPAHs (log octanol-water partition coefficient <3) to the Σ7OPAH concentrations. We identified mean annual precipitation (Spearman ρ = .33, p < .001, n = 143) and clay concentrations (ρ = .55, p < .001, n = 33) as important drivers of the Σ7OPAH/Σ16EPA-PAH concentration ratios. Our results indicate that at low PAH contamination levels, secondary sources contribute considerably and to a variable extent to total OPAH concentrations, whereas at Σ16EPA-PAH contamination levels >400 ng g-1 , there was a nearly constant Σ7OPAH/Σ16EPA-PAH ratio (0.08 ± 0.005 [SE], n = 80) determined by their combustion sources.

250-year records of mercury and trace element deposition in two lakes from Cajas National Park, SW Ecuadorian Andes.

Historical records of trace elements in lake sediments provide source-to-sink information about potentially toxic pollutants across space and time. We investigated two lakes located at different elevations in the Ecuadorian Andes to understand how trace element fluxes are related to (i) geology, (ii) erosion in the watersheds, and (iii) local point sources and atmospheric loads. In remote Lake Fondococha (4150 m a.s.l.), total Hg fluxes stay constant between ca. 1760 and 1950 and show an approximately 4.4-fold increase between pre-1950 and post-1950 values. The post-1950 increase in fluxes of other trace elements (V, Cr, Co, Ni, Cu, Zn, As, Cd, and Pb) is lower (2.1-3.0-fold) than for Hg. Mostly lithogenic sources and enhanced soil erosion contribute to their post-1950 increase (lithogenic contribution: > 85%, Hg: ~ 58%). Average post-1950 Hg fluxes are approximately 4.3 times higher in peri-urban Lake Llaviucu (3150 m a.s.l.) than in the remote Lake Fondococha. Post-1950 fluxes of the other trace elements showed larger differences between Lakes Fondococha and Llaviucu (5.2 < 25-29.5-fold increase; Ni < Pb-Cd). The comparison of the post-1950 average trace element fluxes that are derived from point and airborne sources revealed 5-687 (Hg-Pb) times higher values in Lake Llaviucu than in Lake Fondococha suggesting that Lake Llaviucu's proximity to the city of Cuenca strongly influences its deposition record (industrial emissions, traffic, caged fishery). Both lakes responded with temporary drops in trace element accumulations to park regulations in the 1970s and 1990s, but show again increasing trends in recent times, most likely caused by increase in vehicular traffic and openings of copper and gold mines around Cajas National Park.

Polycyclic aromatic compounds (PAHs, oxygenated PAHs, nitrated PAHs and azaarenes) in soils from China and their relationship with geographic location, land use and soil carbon fractions.

The assessment of risks arising from polycyclic aromatic compounds (PACs), particularly from the polar PACs [azaarenes (AZAs), oxygenated PAHs (OPAHs), nitrated PAHs (NPAHs)] requires us to understand the drivers of their spatial distribution. We determined the concentrations of 29 PAHs, 4 AZAs, 15 OPAHs and 11 NPAHs and their relationships with land use (urban vs. rural and forest vs. agriculture), climate (Qinghai-Tibetan plateau, temperate, sub tropical and tropical) and three C fractions (soil organic C, char, soot) in 36 mineral topsoils (0-5 cm) of China. The average concentrations±standard deviation of the Σ29PAHs, Σ16PAHs, Σ4AZAs, Σ15OPAHs and Σ11NPAHs were 352 ±â€¯283, 206 ±â€¯215, 5.7 ±â€¯3.7, 108 ±â€¯66.8 and 3.2 ±â€¯3.4 ng g-1, respectively. PAH, OPAH, NPAH and AZA concentrations were frequently not correlated within or across the regions reflecting different sources and turnover of PAHs and their derivatives. Temperate urban soils showed the highest and tropical rural soils the lowest concentrations of PACs. Forest soils had higher PACs concentrations than agricultural soils. Longitude correlated positively with the ∑29PAHs concentrations, because of increasing emissions of PAHs from East to West. The tropical and plateau regions with the lowest PAH concentrations, were dominated by low molecular weight PAHs (LMW-PAHs) with LMW/high molecular weight (HMW)-PAHs ratios >1, while the other two climatic regions with more industrial sites showed the opposite. Latitude correlated with NPAHs likely because of enhanced formation by photochemical reactions during transport in the atmosphere. The concentrations of the ∑29PAHs, ∑4AZAs, ∑15OPAHs, ∑11NPAHs and their individual components were only occasionally correlated with those of carbon fractions (soil organic C, soot and char) suggesting a small role of soil C pool properties in driving PACs concentrations. Our results demonstrate that the strongest drivers of PACs concentrations are land use and distance to PAC emission sources followed by climate and size and properties of the soil organic C pool.

Mutagenicity assessment of aerosols in emissions from domestic combustion processes.

Domestic biofuel combustion is one of the major sources of regional and local air pollution, mainly regarding particulate matter and organic compounds, during winter periods. Mutagenic and carcinogenic activity potentials of the ambient particulate matter have been associated with the fraction of polycyclic aromatic hydrocarbons (PAH) and their oxygenated (OPAH) and nitrogenated (NPAH) derivatives. This study aimed at assessing the mutagenicity potential of the fraction of this polycyclic aromatic compound in particles (PM10) from domestic combustion by using the Ames assays with Salmonella typhimurium TA98 and TA100. Seven biofuels, including four types of pellets and three agro-fuels (olive pit, almond shell and shell of pine nuts), were tested in an automatic pellet stove, and two types of wood (Pinus pinaster, maritime pine, and Eucalyptus globulus, eucalypt) were burned in a traditional wood stove. For this latter appliance, two combustion phases­Devolatilisation and flaming/smouldering­Were characterised separately. A direct-acting mutagenic effect for the devolatilisation phase of pine combustion and for both phases of eucalypt combustion was found. Almond shell revealed a weak direct-acting mutagenic effect, while one type of pellets, made of recycled wastes, and pine (devolatilisation) presented a cytotoxic effect towards strain TA100. Compared to the manually fired appliance, the automatic pellet stove promoted lower polyaromatic mutagenic emissions. For this device, only two of the studied biofuels presented a weak mutagenic or cytotoxic potential.

Polycyclic aromatic hydrocarbons and their derivatives (nitro-PAHs, oxygenated PAHs, and azaarenes) in PM2.5 from Southern European cities.

Atmospheric particulate matter (PM2.5) samples were collected over two one month periods during winter and summer in three Southern European cities (Oporto - traffic site, Florence - urban background, Athens - suburban). Concentrations of 27 polycyclic aromatic hydrocarbons (PAHs), 15 nitro-PAHs (NPAHs), 15 oxygenated-PAHs (OPAHs) and 4 azaarenes (AZAs) were determined. On average, the winter-summer concentrations of ΣPAHs were 16.3-5.60, 7.75-3.02 and 3.44-0.658ngm-3 in Oporto, Florence and Athens, respectively. The corresponding concentrations of ΣNPAHs were 15.8-9.15, 10.9-3.36 and 15.9-2.73ngm-3, whilst ΣOPAHs varied in the ranges 41.8-19.0, 11.3-3.10 and 12.6-0.704ngm-3. Concentrations of ΣAZAs were always below 0.5ngm-3. Irrespective of the city, the dominant PAHs were benzo[b+j+k]fluoranthene, retene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene. The most abundant OPAH in all cities was 1,8-naphthalic anhydride, whereas 5-nitroacenaphthene was the prevailing NPAH. The ΣOPAHs/ΣPAHs and ΣNPAHs/ΣPAHs were higher in summer than in winter, suggesting increasing formation of derivatives by photochemical degradation of PAHs. Molecular diagnostic ratios suggested that, after traffic, biomass burning was the dominant emission source. Apart from being influenced by seasonal sources, the marked differences between winter and summer may indicate that these diagnostic ratios are particularly sensitive to photodegradation, and thus should be applied and interpreted cautiously. The lifetime excess cancer risk from inhalation was, in part, attributable to PAH derivatives, acclaiming the need to include these compounds in regular monitoring programmes. On average, 206, 88 and 26 cancer cases per million people were estimated, by the World Health Organisation method, for the traffic-impacted, urban background and suburban atmospheres of Oporto, Florence and Athens, respectively.

Effects of polycyclic aromatic compounds in fine particulate matter generated from household coal combustion on response to EGFR mutations in vitro.

Induction of PM2.5-associated lung cancer in response to EGFR-tyrosine kinase inhibitors (EGFR-TKI) remains unclear. Polycyclic aromatic hydrocarbons (PAHs) and their polar derivatives (oxygenated PAHs: OPAHs and azaarenes: AZAs) were characterized in fine particulates (PM2.5) emitted from indoor coal combustion. Samples were collected in Xuanwei (Yunnan Province), a region in China with a high rate of lung cancer. Human lung adenocarcinoma cells A549 (with wild-type EGFR) and HCC827 (with EGFR mutation) were exposed to the PM2.5, followed by treatment with EGFR-TKI. Two samples showed significant and dose-dependent reduction in the cell viability in A549. EGFR-TKI further demonstrated significantly decreased in cell viability in A549 after exposure to the coal emissions. Chrysene and triphenylene, dibenzo[a,h]anthracene, benzo[ghi]perylene, azaarenes and oxygenated polycyclic aromatic hydrocarbons (carbonyl-OPAHs) were all associated with EGFR-TKI-dependent reduced cell viability after 72-h exposure to the PM2.5. The findings suggest the coal emissions could influence the response of EGFR-TKI in lung cancer cells in Xuanwei.

Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) in urban soils of Bratislava, Slovakia: patterns, relation to PAHs and vertical distribution.

We determined concentrations, sources, and vertical distribution of OPAHs and PAHs in soils of Bratislava. The ∑14 OPAHs concentrations in surface soil horizons ranged 88-2692 ng g(-1) and those of ∑34 PAHs 842-244,870 ng g(-1). The concentrations of the ∑9 carbonyl-OPAHs (r=0.92, p=0.0001) and the ∑5 hydroxyl-OPAHs (r=0.73, p=0.01) correlated significantly with ∑34 PAHs concentrations indicating the close association of OPAHs with parent-PAHs. OPAHs were quantitatively dominated by 9-fluorenone, 9,10-anthraquinone, 1-indanone and benzo[a]anthracene-7,12-dione. At several sites, individual carbonyl-OPAHs had higher concentrations than parent PAHs. The concentration ratios of several OPAHs to their parent-PAHs and contribution of the more soluble OPAHs (1-indanone and 9-fluorenone) to ∑14 OPAHs concentrations increased with soil depth suggesting that OPAHs were faster vertically transported in the study soils by leaching than PAHs which was supported by the correlation of subsoil:surface soil ratios of OPAH concentrations at several sites with K(OW).

Polycyclic aromatic hydrocarbons (PAHs) and their oxygen-containing derivatives (OPAHs) in soils from the Angren industrial area, Uzbekistan.

We measured the concentrations and depth distribution (0-10, 10-20 cm) of 31 PAHs and 12 OPAHs in soils at eleven equidistant sampling points along a 20-km transect in the Angren industrial region (coal mine, power plant, rubber factory, gold mine), Uzbekistan to gain an insight into their concentrations, sources, and fate. Concentrations of all compounds were mostly much higher in the 0-10 cm than in the 10-20 cm layer except in disturbed soil close to the coal mine. Proximity to one of the industrial emitters was the main determinant of PAH and OPAH concentrations. The Sigma31PAHs concentrations correlated positively with the Sigma7 carbonyl-OPAH (r=0.98, p<0.01), Sigma5 hydroxyl-OPAH (r=0.72, p<0.05), and with industrially emitted trace metals in the topsoil, identifying industrial emissions as their common source. Concentrations of several OPAHs were higher than their parent PAHs, but their vertical distribution in soil suggested only little higher mobility of OPAHs than their corresponding parent PAHs.

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia.

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g(-1). PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C(org)) concentrations.