Polycyclic aromatic hydrocarbons (PAHs) in soils of an industrial area in semi-arid Uzbekistan: spatial distribution, relationship with trace metals and risk assessment.

The concentrations, composition patterns, transport and fate of PAHs in semi-arid and arid soils such as in Central Asia are not well known. Such knowledge is required to manage the risk posed by these toxic chemicals to humans and ecosystems in these regions. To fill this knowledge gap, we determined the concentrations of 21 parent PAHs, 4,5-methylenephenanthrene, 6 alkylated PAHs, and biphenyl in soils from 11 sampling locations (0-10, 10-20 cm soil depths) along a 20-km transect downwind from the Almalyk metal mining and metallurgical industrial complex (Almalyk MMC), Uzbekistan. The concentrations of Σ29 PAHs and Σ16 US-EPA PAHs were 41-2670 ng g-1 and 29-1940 ng g-1, respectively. The highest concentration of Σ29 PAHs occurred in the immediate vicinity of the copper smelting factory of the Almalyk MMC. The concentrations in topsoil decreased substantially to a value of ≤ 200 ng g-1 (considered as background concentration) at ≥ 2 km away from the factory. Low molecular weight PAHs dominated the PAH mixtures at less contaminated sites and high molecular weight PAHs at the most contaminated site. The concentration of Σ16 US-EPA PAHs did not exceed the precautionary values set by the soil quality guidelines of, e.g., Switzerland and Germany. Similarly, the benzo[a]pyrene equivalent concentration in soils near the Almalyk MMC did not exceed the value set by the Canadian guidelines for the protection of humans from carcinogenic PAHs in soils. Consequently, the cancer risk due to exposure to PAHs in these soils can be considered as low.

Polycyclic aromatic compounds (PAHs, oxygenated PAHs, nitrated PAHs, and azaarenes) in air from four climate zones of China: Occurrence, gas/particle partitioning, and health risks.

Polycyclic aromatic compounds (PACs) such as polycyclic aromatic hydrocarbons (PAHs) and their derivatives [oxygenated PAHs (OPAHs), nitrated PAHs (NPAHs), and azaarenes (AZAs)] are toxic and ubiquitous air pollutants. In this study, the concentrations of these PACs were determined in air obtained in spring and autumn of 2012 from urban and rural areas of the Tibetan Plateau, temperate, subtropical, and tropical climate zones in China. Average concentrations (gaseous + particulate) of ∑29PAHs, ∑15OPAHs, ∑11NPAHs, and ∑4AZAs were 928 ± 658, 54 ± 45, 5.3 ± 4.4, 14 ± 11 ng m-3 and 995 ± 635, 67 ± 38, 8.4 ± 6.1, 24 ± 16 ng m-3 in spring and autumn, respectively. Various C fractions and latitude correlated significantly with the concentrations and ratios of PACs. The slopes of the regression of gas-particle partition coefficients (Kp) of PACs on their sub-cooled liquid vapor pressures (PL0), indicated both adsorption and absorption to total suspended particles (TSP) for PAHs, OPAHs, and NPAHs in the four studied climatic zones. This result was further supported by comparing the fractions of PACs in TSP calculated from field data with those predicted by the Junge-Pankow adsorption and KOA absorption models. The concentration ratios of most OPAHs or NPAHs to their parent PAHs and of benzo[e]pyrene/benzo[a]pyrene were higher in autumn than in spring and increased with remoteness from point sources. This suggests enhanced secondary formation of PAH derivatives due to the elevated photochemical activity in autumn and longer ageing of air and associated transformation of PACs during their long-distance transport from source regions (urban sites) to rural sites. Lifetime lung cancer risk estimated from PACs ranged from 0.8 ± 0.6 to 3.1 ± 1.0 (×10-3), exceeding the value (10-5) recommended by the WHO. Gaseous PACs contributed substantially to the estimated cancer risks and their contributions increased with decreasing latitude in China.

A 150-year record of black carbon (soot and char) and polycyclic aromatic compounds deposition in Lake Phayao, north Thailand.

An improved understanding of the historical variation in the emissions and sources (biomass burning, BB vs. fossil fuel, FF combustion) of soot and char, the two components of black carbon (BC), and polycyclic aromatic compounds (PACs) may help in assessing the environmental effects of the Atmospheric Brown Cloud (ABC) in SE Asia. We therefore determined historical variations of the fluxes of soot, char, and PACs (24 polycyclic aromatic hydrocarbons (PAHs), 12 oxygenated PAHs (OPAHs), and 4 azaarenes) in a dated sediment core (covering the past ∼150 years) of Phayao Lake in Thailand. The soot fluxes have been increasing in recent times, but at a far lower rate than previously estimated based on BC emission inventories. This may be associated with a decreasing BB contribution as indicated by the decreasing char fluxes from old to young sediments. The fluxes of high- and low-molecular-weight (HMW and LMW) PAHs, OPAHs, and azaarenes all sharply increased after ∼1980, while the ΣLMW-/ΣHMW-PAHs ratios decreased, further supporting the reduction in BB contribution at the expense of increasing FF combustion emissions. We also suggest that the separate record of char and soot, which has up to now not been done in aerosol studies, is useful to assess the environmental effects of ABC because of the different light-absorbing properties of these two BC components. Our results suggest that besides the establishment of improved FF combustion technology, BB must be further reduced in the SE Asian region in order to weaken the ABC haze.

Using isotopes to trace freshly applied cadmium through mineral phosphorus fertilization in soil-fertilizer-plant systems.

Applications of mineral phosphorus (P) fertilizer can lead to cadmium (Cd) accumulation in soils and can increase Cd concentrations in edible crop parts. To determine the fate of freshly applied Cd, a Cd source tracing experiment was conducted in three soil-fertilizer-wheat systems by using a mineral P fertilizer labeled with the radio isotope 109Cd and by exploiting natural differences in Cd stable isotope compositions (δ114/110Cd). Source tracing with stable isotopes overestimated the proportion of Cd in plants derived from the P fertilizer, because the isotope ratios of the sources were not sufficiently distinct from those of the soils. Despite indistinguishable extractable Cd pools between control and treatments, the addition of P fertilizer resulted in a more negative apparent isotope fractionation between soil and wheat. Overall, the radio isotope approach provided more robust results and revealed that 6.5 to 15% of the Cd in the shoot derived from the fertilizer. From the introduced Cd, a maximum of 2.2% reached the wheat shoots, whilst 97.8% remained in the roots and soils. The low recoveries of the fertilizer derived Cd suggest that continuous P fertilizer application in the past decades can lead to a build-up of a residual Cd pool in soils.

Zinc isotope fractionation during grain filling of wheat and a comparison of zinc and cadmium isotope ratios in identical soil-plant systems.

Remobilization of zinc (Zn) from shoot to grain contributes significantly to Zn grain concentrations and thereby to food quality. On the other hand, strong accumulation of cadmium (Cd) in grain is detrimental for food quality. Zinc concentrations and isotope ratios were measured in wheat shoots (Triticum aestivum) at different growth stages to elucidate Zn pathways and processes in the shoot during grain filling. Zinc mass significantly decreased while heavy Zn isotopes accumulated in straw during grain filling (Δ66 Znfull maturity-flowering  = 0.21-0.31‰). Three quarters of the Zn mass in the shoot moved to the grains, which were enriched in light Zn isotopes relative to the straw (Δ66 Zngrain-straw -0.21 to -0.31‰). Light Zn isotopes accumulated in phloem sinks while heavy isotopes were retained in phloem sources likely because of apoplastic retention and compartmentalization. Unlike for Zn, an accumulation of heavy Cd isotopes in grains has previously been shown. The opposing isotope fractionation of Zn and Cd might be caused by distinct affinities of Zn and Cd to oxygen, nitrogen, and sulfur ligands. Thus, combined Zn and Cd isotope analysis provides a novel tool to study biochemical processes that separate these elements in plants.

Cadmium Isotope Fractionation in Soil-Wheat Systems.

Analyses of stable metal isotope ratios constitute a novel tool in order to improve our understanding of biogeochemical processes in soil-plant systems. In this study, we used such measurements to assess Cd uptake and transport in wheat grown on three agricultural soils under controlled conditions. Isotope ratios of Cd were determined in the bulk C and A horizons, in the Ca(NO3)2-extractable Cd soil pool, and in roots, straw, and grains. The Ca(NO3)2-extractable Cd was isotopically heavier than the Cd in the bulk A horizon (Δ(114/110)Cdextract-Ahorizon = 0.16 to 0.45‰). The wheat plants were slightly enriched in light isotopes relative to the Ca(NO3)2-extractable Cd or showed no significant difference (Δ(114/110)Cdwheat-extract = -0.21 to 0.03‰). Among the plant parts, Cd isotopes were markedly fractionated: straw was isotopically heavier than roots (Δ(114/110)Cdstraw-root = 0.21 to 0.41‰), and grains were heavier than straw (Δ(114/110)Cdgrain-straw = 0.10 to 0.51‰). We suggest that the enrichment of heavy isotopes in the wheat grains was caused by mechanisms avoiding the accumulation of Cd in grains, such as the chelation of light Cd isotopes by thiol-containing peptides in roots and straw. These results demonstrate that Cd isotopes are significantly and systematically fractionated in soil-wheat systems, and the fractionation patterns provide information on the biogeochemical processes in these systems.

Occurrence, gas/particle partitioning and carcinogenic risk of polycyclic aromatic hydrocarbons and their oxygen and nitrogen containing derivatives in Xi'an, central China.

29 parent- and alkyl-polycyclic aromatic hydrocarbons (PAHs), 15 oxygenated-PAHs (OPAHs), 11 nitrated-PAHs (NPAHs) and 4 azaarenes (AZAs) in both the gaseous and particulate phases, as well as the particulate-bound carbon fractions (organic carbon, elemental carbon, char, and soot) in ambient air sampled in March and September 2012 from an urban site in Xi'an, central China were extracted and analyzed. The average concentrations (gaseous+particulate) of ∑29PAHs, ∑15OPAHs, ∑11NPAHs and ∑4AZAs were 1267.0 ± 307.5, 113.8 ± 46.1, 11.8 ± 4.8 and 26.5 ± 11.8 ng m(-3) in March and 784.7 ± 165.1, 67.2 ± 9.8, 9.0 ± 1.5 and 21.6 ± 5.1 ng m(-3) in September, respectively. Concentrations of ∑29PAHs, ∑15OPAHs and ∑11NPAHs in particulates were significantly correlated with those of the carbon fractions (OC, EC, char and soot). Both absorption into organic matter in particles and adsorption onto the surface of particles were important for PAHs and OPAHs in both sampling periods, with more absorption occurring in September, while absorption was always the most important process for NPAHs. The total carcinogenic risk of PAHs plus the NPAHs was higher in March. Gaseous compounds, which were not considered in most previous studies, contributed 29 to 44% of the total health risk in March and September, respectively.

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (alkyl-PAHs, oxygenated-PAHs, nitrated-PAHs and azaarenes) in urban road dusts from Xi'an, Central China.

Urban road dusts are carriers of polycyclic aromatic compounds (PACs) and are therefore considered to be a major source of contamination of other environmental compartments and a source of exposure to PACs for urban populations. We determined the occurrence, composition pattern and sources of several PACs (29 alkyl- and parent-PAHs, 15 oxygenated-PAHs (OPAHs), 4 azaarenes (AZAs), and 11 nitrated-PAHs (NPAHs)) in twenty urban road dusts and six suburban surface soils (0-5cm) from Xi'an, central China. The average concentrations of ∑29PAHs, ∑4AZAs, ∑15OPAHs, and ∑11NPAHs were 15767, 673, 4754, and 885 n gg(-1) in road dusts and 2067, 784, 854, and 118 ng g(-1) in surface soils, respectively. The concentrations of most individual PACs were higher in street dusts than suburban soils, particularly for PACs with molecular weight>192 g mol(-1). The enrichment factors of individual PACs were significantly positively correlated with log KOA and log KOW, indicating an increasing deposition and co-sorption of the PACs in urban dusts with decreasing volatility and increasing hydrophobicity. Significant correlations between the concentrations of individual and sum of PACs, carbon fractions (soot and char), and source-characteristic PACs (combustion-derived PAHs and retene, etc.), indicated that PAHs, OPAHs and AZAs were mostly directly emitted from combustion activities and had similar post-emission fates, but NPAHs were possibly more intensely photolyzed after deposition as well as being emitted from vehicle exhaust sources. The incremental lifetime cancer risk (ILCR) resulting from exposure to urban dust bound-PACs was higher than 10(-6), indicating a non-negligible cancer risk to residents of Xi'an.

Polycyclic aromatic compounds (PAHs and oxygenated PAHs) and trace metals in fish species from Ghana (West Africa): bioaccumulation and health risk assessment.

We report the concentrations of 28 PAHs, 15 oxygenated PAHs (OPAHs) and 11 trace metals/metalloids (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, and Zn) in muscle and gut+gill tissues of demersal fishes (Drapane africana, Cynoglossus senegalensis and Pomadasys peroteti) from three locations along the coast of the Gulf of Guinea (Ghana). The concentrations of ∑28PAHs in muscle tissues averaged 192ngg(-1) dw (range: 71-481ngg(-1) dw) and were not statistically different between locations. The concentrations of ∑28 PAHs were higher in guts+gills than in muscles. The PAH composition pattern was dominated by low molecular weight compounds (naphthalene, alkyl-naphthalenes and phenanthrene). All fish tissues had benzo[a]pyrene concentrations lower than the EU limit for food safety. Excess cancer risk from consumption of some fish was higher than the guideline value of 1×10(-6). The concentrations of ∑15 OPAHs in fish muscles averaged 422ngg(-1) dw (range: 28-1715ngg(-1)dw). The ∑15 OPAHs/∑16 US-EPA PAHs concentration ratio was >1 in 68% of the fish muscles and 100% of guts+gills. The log-transformed concentrations of PAHs and OPAHs in muscles, guts+gills were significantly (p<0.05) correlated with their octanol-water partitioning coefficients, strongly suggesting that equilibrium partitioning from water/sediment into fish tissue was the main mechanism of bioaccumulation. The trace metal concentrations in the fish tissues were in the medium range when compared to fish from other parts of the world. The concentrations of some trace metals (Cd, Cu, Fe, Mn, Zn) were higher in guts+gills than in muscle tissues. The target hazard quotients for metals were<1 and did not indicate a danger to the local population. We conclude that the health risk arising from the consumption of the studied fish (due to their PAHs and trace metals content) is minimal.

PM2.5-bound oxygenated PAHs, nitro-PAHs and parent-PAHs from the atmosphere of a Chinese megacity: seasonal variation, sources and cancer risk assessment.

Polycyclic aromatic compounds (PACs) in air particulate matter contribute considerably to the health risk of air pollution. The objectives of this study were to assess the occurrence and variation in concentrations and sources of PM2.5-bound PACs [Oxygenated PAHs (OPAHs), nitro-PAHs and parent-PAHs] sampled from the atmosphere of a typical Chinese megacity (Xi'an), to study the influence of meteorological conditions on PACs and to estimate the lifetime excess cancer risk to the residents of Xi'an (from inhalation of PM2.5-bound PACs). To achieve these objectives, we sampled 24-h PM2.5 aerosols (once in every 6 days, from 5 July 2008 to 8 August 2009) from the atmosphere of Xi'an and measured the concentrations of PACs in them. The PM2.5-bound concentrations of Σcarbonyl-OPAHs, ∑hydroxyl+carboxyl-OPAHs, Σnitro-PAHs and Σalkyl+parent-PAHs ranged between 5-22, 0.2-13, 0.3-7, and 7-387 ng m(-3), respectively, being markedly higher than in most western cities. This represented a range of 0.01-0.4% and 0.002-0.06% of the mass of organic C in PM2.5 and the total mass of PM2.5, respectively. The sums of the concentrations of each compound group had winter-to-summer ratios ranging from 3 to 8 and most individual OPAHs and nitro-PAHs had higher concentrations in winter than in summer, suggesting a dominant influence of emissions from household heating and winter meteorological conditions. Ambient temperature, air pressure, and wind speed explained a large part of the temporal variation in PACs concentrations. The lifetime excess cancer risk from inhalation (attributable to selected PAHs and nitro-PAHs) was six fold higher in winter (averaging 1450 persons per million residents of Xi'an) than in summer. Our results call for the development of emission control measures.

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.