Polycyclic aromatic hydrocarbons: bees, honey and pollen as sentinels for environmental chemical contaminants

Three beehive matrices, sampled in six different apiaries from West France, were analyzed for the presence of four polycyclic aromatic hydrocarbons (PAH4: benzo[a]pyrene, benzo[a]anthracene, benzo[b]fluoranthene and chrysene). Samples were collected during four different periods in both 2008 and 2009. Honey samples showed the lowest levels of PAH4 contamination (min = 0.03 μg kg⁻¹; max = 5.80 μg kg⁻¹; mean = 0.82 μg kg⁻¹; Sd = 1.17). Bee samples exhibited higher levels of PAH4 contamination (min = 0.32 μg kg⁻¹; max = 73.83 μg kg⁻¹; mean = 7.03 μg kg⁻¹; Sd = 17.83) with a great dispersion of the concentrations due to four main events of high concentrations. Pollen samples showed only one major episode with the highest PAH4 concentration found (min = 0.33 μg kg⁻¹; max = 129.41 μg kg⁻¹; mean = 7.10 μg kg⁻¹; Sd = 22.28). The PAH4 concentrations found were significantly influenced by the landscape context for all beehive samples.     

Structural and optical characterization of dissolved organic matter from the lower Athabasca River, Canada

Dissolved organic matter (DOM) is a ubiquitous constituent of natural waters and is comprised of a variety of chemically heterogeneous molecular structures and functional groups. DOM is often considered to be a major ligand for metals in most natural waters and its reactivity is thought to be strongly dependent on its chemical composition and structure. In this study, a combination of UV/visible, emission excitation matrix fluorescence (EEM) and ¹H NMR spectroscopies were used to characterize DOM from the Athabasca River (Alberta, Canada). The chemical characterization of river DOM showed that the most upstream samples located in agricultural areas were blue-shifted and less aromatic and contained more hydrogens connected with oxygen functional groups than those in the wetland dominated area in the Athabasca oil sand deposit region. The presence of paramagnetic ions (Fe and Al) was not found to significantly affect the structural composition of DOM as revealed by ¹H NMR. Such change in the quality of DOM may have a profound impact on metal binding in the Athabasca River watershed.     

Desorption of polycyclic aromatic hydrocarbons from field-contaminated soil to a two-dimensional hydrophobic surface before and after bioremediation

This study investigated environmental distributions and production mechanisms of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) in the sediments from some tidal flats located in Asia. Cl-PAHs were found in sediments taken from Arao tidal flat, Kikuchigawa River and Shirakawa River. The range of ∑Cl-PAHs was from 25.5 to 483 pg g⁻¹ for Kikuchigawa River and Arao tidal flat, respectively.Concentrations of PAHs and Cl-PAHs showed no significant correlations (r = 0.134). This result suggests that the origins of these compounds differ. In the identified Cl-PAH isomers, the most abundant Cl-PAH isomer was 9,10-dichloroanthracene (9,10-di-Cl-ANT) in the three sites. In general, concentrations of Cl-ANTs in the coastal environment are about 3-5 orders of magnitude lower than those of anthracene (ANT). However, concentration ratios between Cl-ANTs and ANT (Cl-ANTs/ANT) in the sediments ranged from 4.1% to 24.6%. This result indicated that Cl-PAHs were not generated under industrial processes but the high concentration ratios have resulted from the contribution of photochemical production of Cl-ANTs in the sediments because ANT is known to have high photochemical reactivity.For examining this phenomenon, ANT adsorbed onto glass beads was irradiated with UV under the mimicked field conditions of tidal flats. As a result, it was noticed that, while chlorinated derivatives were negligible in a light-controlled group, production of 2-Cl-ANT, 9-Cl-ANT and 9,10-diCl-ANT on the irradiated surface were found in this study. These results suggest that photochemical reaction of PAHs can be a potential source of the occurrence of Cl-PAHs in the coastal environment.     

Sources and distribution of polycyclic aromatic hydrocarbons in sediments from the Spanish northern continental shelf. Assessment of spatial and temporal trends

The distribution of polycyclic aromatic hydrocarbons was determined in surface sediments collected at 36 stations along the Spanish Northern continental shelf in March and September 2003, and February 2005. Concentrations of PAHs (Σ13 parent components) were in the range of 22-47528 μg/kg dw, the highest values corresponding to coastal urban-industrial hotspots and decreasing offshore. Sediment quality guidelines (SQGs) showed that concentrations of total PAHs were below the threshold effect level (TEC) in 27 stations (81%) and above in 7, two of which (Gijon and Bilbao) were above the probable effect concentration (PEC). The detailed study of diagnostic ratios suggested a rather uniform mixture of petrogenic and pyrolytic PAH sources along the continental shelf, with a slight decrease of the latter moving westwards and offshore. In order to assess the incidence of sediment sampling on the variability of the results, selected stations were also monitored in February and September 2004 and September 2005. The average field variance of the values obtained for each station was 31% that decreased to 23% when the values were normalized to TOC.     

Oil Identification Based on a Goodness-of-Fit Metric Applied to Hydrocarbon Analysis Results

Assessment of environmental damage following accidental oil spills requires reliable oil identification methods. Results from hydrocarbon analyses of environmental samples are often difficult to interpret, because of the changes in oil composition (or weathering) that follows release into the environment, and because of confounding by hydrocarbons from other sources. To a first-order approximation, weathering proceeds according to simple first-order loss-rate (FOLR) kinetics for polycyclic aromatic hydrocarbons (PAH) based on molecular size. This relationship between relative weathering rate and molecular size can be exploited to infer the initial PAH composition of spilled oils, and this information can be combined with results for weathering-invariant analytes to substantially increase the precision and accuracy of hydrocarbon source recognition methods. The approach presented here evaluates a goodness-of-fit metric between the measured hydrocarbon composition of an environmental sample and a suspected source, after correcting for PAR weathering losses based on FOLR kinetics. Variability from analytical and sampling error may thus be accounted for, and source identifications can be expressed as objective probability statements. This approach is illustrated by application to four independent case studies.     

Temperature-dependent sorption of polycyclic aromatic hydrocarbons on natural and treated sediments

In aqueous environment temperature is considered to play a significant role in the sorption process of polycyclic aromatic hydrocarbons (PAHs) and its influence on the sorption equilibrium is indicative of sorption energies and mechanisms. In this study, sorptions of five PAHs on three heterogeneous sorbents including one river sediment (YHR), one estuary sediment (YRD) and one treated sediment with organic matter removed (IM) were carried out at a range of temperature from 5 °C to 35 °C. Stronger sorptions were observed at lower temperatures, with the equilibrium sorption coefficient K_d increasing 2-5 times as the temperature decreases 30 °C. The increase of K_d value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of K_d in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔH_S) for the sorption process was calculated and the values were observed to be negative for all of the interactions, suggesting that the exothermal sorption of PAHs inversely dependents on temperature. Based on the values of ΔH_S, van der Waals forces were inferred as the main sorption mechanism for the PAHs, especially on the YHR sediment which contained more organic matter. For sorption of larger size PAHs on the sorbents with low organic matter, specific interactions were deduced to contribute to the overall sorption.     

Temporal and geographical genetic variation in the amphipod Melita plumulosa (Crustacea: Melitidae): Link of a localized change in haplotype frequencies to a chemical spill

Anthropogenic effects such as contamination affect the genetic structure of populations. This study examined the temporal and geographical patterns of genetic diversity among populations of the benthic crustacean amphipod Melita plumulosa in the Parramatta River (Sydney, Australia), following an industrial chemical spill. The spill of an acrylate/methacrylate co-polymer in naphtha solvent occurred in July 2006. M. plumulosa were sampled temporally between December 2006 and November 2009 and spatially in November 2009. Genetic variation was examined at the mitochondrial cytochrome c oxidase subunit I locus. Notably, nucleotide diversity was low and Tajima’s D was significantly negative amongst amphipods collected immediately downstream from the spill for 10 months. We hypothesize that the spill had a significant localized effect on the genetic diversity of M. plumulosa. Alternate explanations include an alternate and unknown toxicant or a localized sampling bias. Future proposed studies will dissect these alternatives.     

WATER QUALITY IN A MEDITERRANEAN MARINE PROTECTED AREA (NORTH SPORADES ISLANDS, GREECE)

Pollution in the marine protected area of North Sporades Islands was investigated in July 1997. Salinity, temperature, dissolved oxygen, dissolved inorganic nutrients, organic carbon, hydrocarbons as well as dissolved and particulate trace metals were determined at 15 offshore and coastal stations. Dissolved organic carbon and inorganic nutrient concentrations indicate the mesotrophic character of the investigated waters. The dissolved forms of nitrogen were slightly higher at coastal stations. Dissolved and particulate Cu, Zn and Ni, were higher in coastal stations, whereas concentrations of Pb were generally low and likely of atmospheric origin. Dissolved/Dispersed petroleum hydrocarbons (DDPH) were close to detection limits at all stations. Temperature and salinity vertical profiles, nutrient and trace metal concentrations revealed the presence of a slight influence of the Black Sea water coming from Dardanelles straits.     

Integration of chemical and biological methods: A case study of polycyclic aromatic hydrocarbons pollution monitoring in Shandong Peninsula, China

Polycyclic aromatic hydrocarbons(PAHs), as persistent toxic substances(PTS), have been widely monitored in coastal environment, including seawater and sediment. However, scientific monitoring methods, like ecological risk assessment and integrated biomarker response, still need massive researches to verify their availabilities. This study was performed in March, May, August and October of 2018 at eight sites, Yellow River estuary(S1), Guangli Port(S2), Xiaying(S3), Laizhou(S4), Inner Bay(S5), Ou...     

多环芳烃的零阶价分子连接性指数与正-辛醇/水分配系数

本文建立了准确预测多环芳烃(PAHs)及其烷基衍生物的正-辛醇/水分配系数(Kow)模型。模型表明PAHs的分配性质可用零阶价分子连接性指数(~°x~v)描述,~°x~v数值与PAHs的logKow成正比。应用本模型可以预测大范围PAHs的logKow值。