Microbial metabolic routes in metagenome assembled genomes are mirrored by the mass balance of polycyclic aromatic hydrocarbons in a high altitude lake.

Semivolatile organic pollutants have potential for long range atmospheric transport and can thus reach pristine remote lakes by atmospheric deposition. Polycyclic aromatic hydrocarbons (PAHs) are among the most abundant and toxic semivolatile pollutants affecting lakes, however, the main factors controlling their fate are still poorly known. Here we show two contrasting lines of evidence for the importance of microbial degradation on the environmental fate of PAHs in a high altitude deep lake. The first evidence is given by an assessment of the metagenomes from surface and deep waters from Lake Redon (Pyrenees Mountains), which shows the occurrence of the initial ring hydroxylating dioxygenases as well as other PAH degrading genes from the complete metabolic route of PAH degradation. The second line of evidence is by the application of an environmental fate model for PAHs to Lake Redon under two contrasting scenarios considering the inclusion or not of degradation. When degradation is included in the model, PAH concentrations in the sediment are predicted within a factor of two of those measured in Lake Redon. Finally, the extent of the degradation sink is quantified and compared to other cycling PAH fluxes in the lake.

Seasonal fluxes and temperature-dependent accumulation of persistent organic pollutants in lakes: the role of internal biogeochemical cycling.

A dynamic flux model for lakes taking into account the interactions between atmospheric depositional and biogeochemical processes (BIODEP model) was used to assess the importance of internal cycling and biogeochemical processes with respect to accumulation of four different polychlorinated biphenyls (PCBs) (congeners 28, 52, 101 and 153) in Lake Redo, a high-altitude lake in the Spanish Pyrenees. To investigate the effect of temperature on sediment accumulation, the model was run at different temperatures and corresponding sediment inventories were plotted vs. reciprocal temperature. In line with measurements from a previous study looking at sediment inventories of 19 European high-altitude lakes (MOLAR study), we found a stronger temperature dependence of lake sediment concentrations for the less volatile/less soluble PCBs. Seasonal and annual mass balances were investigated and highlighted the importance of internal lake processes controlling the differences in sediment accumulation for the different PCB congeners. For example, the higher temperature dependence of sediment inventories for the high chlorinated congeners is due to the fast dynamics of water-to-sediment transport in comparison to atmospheric deposition processes.

Temporal trends of polycyclic aromatic hydrocarbons in the U.K. atmosphere: 1991-2005.

Internationally there are few long-term air monitoring programs, which are necessary to assess the effectiveness of source abatement measures as required underthe UNECE POPs protocol. In the United Kingdom, the Toxic Organic Micropollutants (TOMPS) program, funded by the Department for Environment, Food, and Rural Affairs (Defra), was started in 1991 and includes regular monitoring of a range of compounds including polycyclic aromatic hydrocarbons (PAHs). In this study, the time series (1991-2005) of atmospheric concentrations of 15 PAHs at six U.K. monitoring sites were investigated. Most show a statistically significant decrease in PAH levels over time, broadly consistent with the reported decline in emissions. Higher levels of heavier PAHs were noted in winter than in summer at most sites. At one coastal site, higher levels of lighter PAHs were noted in summer, possibly due to temperature-driven outgassing of these compounds from seawater. Current annual averages of benzo[a]pyrene are below the recently introduced annual air quality standard of 0.25 ng m(-3) at all sites, although quarterly averages have exceeded 0.25 ng m(-3) in recent years but only at the urban sites in winter. The atmospheric signature of total PAHs closely mirrors the emission signature, which lends strength to the idea that levels of PAHs in air are still mostly influenced by direct/local sources.

Modelling the dynamic air-water-sediment coupled fluxes and occurrence of polychlorinated biphenyls in a high altitude lake.

The BIODEP model in terms of atmosphere-lake interactions was developed. The model was applied to an oligotrophic, dimictic high altitude lake (Lake Redo, Pyrenees) for a range of polychlorinated biphenyl (PCB) congeners. High altitude lakes, which receive their contaminant inputs uniquely from the atmosphere through long-range atmospheric transport, provide ideal controlled environments for the study of the interactions between atmospheric depositional and water column biogeochemical processes. The BIODEP model was able to predict dissolved water concentrations and PCB accumulation in the lake sediment within a factor of 2. This shows that the BIODEP model captures the essential processes driving the sink of POPs in high altitude lakes and that POP occurrence in the lake is driven by direct atmospheric inputs with limited influence from the watershed. An important seasonal variability in water column concentrations is predicted which should have important implications in sampling strategies. Furthermore, it is shown that diffusive air-water exchange dominated the PCB dynamics in the lake, especially for the less chlorinated biphenyls.

Further studies on the latitudinal and temporal trends of persistent organic pollutants in Norwegian and U.K. background air.

Data are presented for PBDEs, PCBs, and selected organochlorine compounds, measured at background locations by passive air samplers (semipermeable membrane devices, SPMDs) along a latitudinal transect from the south of the U.K. to the north of Norway during 2000-2002. This work is part of an ongoing air sampling campaign in which PCB data were previously obtained in 1994-1996 and 1998-2000. Comparisons of the masses of chemicals sequestered by the SPMDs during these different time intervals are used to investigate spatial and temporal trends. The study yielded examples of compounds that increase, decrease, or remain uniform with latitude, suggestive of differences in the relative importance of deposition versus atmospheric reaction in controlling their long-range atmospheric transport potential. The main constituents of the penta-BDE product were detected at amounts equivalent to 2.0 (range 1.1-2.5) and 1.1 (0.8-1.6) pg m(-3) for the U.K. and Norway background sites, respectively. Fractionation of PBDEs was observed, because the amounts of lighter BDEs decreased with latitude, while the heavier molecular weight congeners were quite uniformly distributed. In contrast, the sequestered amounts of the lighter PCBs were uniformly distributed with latitude, with heavier PCBs decreasing. Sequestered amounts of hexachlorobenzene increased with latitude. Preliminary PCB atmospheric clearance rates were derived using the 1994-1996, 1998-2000, and 2000-2002 data. They averaged ca. 3.5 years for all congeners/locations. No systematic differences in congeners or locations were noted, supporting the hypothesis that the underlying trends in European background air are still controlled by primary, rather than secondary, sources.

PBDEs in European background soils: levels and factors controlling their distribution.

Surface soils (0-5 cm) from remote/rural woodland (coniferous and deciduous) and grassland locations on a latitudinal transectthrough the United Kingdom and Norway were analyzed for polybrominated diphenyl ethers (PBDEs). Concentrations ranged between 65 and 12 000 sigma(ALL)PBDE ng kg(-1) dry weight. PBDE-47, -99, -100, -153, and -154-the major constituents of the penta-BDE technical product-dominated the average congener pattern of the soils. Indeed, the average congener composition and distribution measured in these European background soils closely matched that reported in the technical penta-BDE product. This is interpreted as evidence that transfer of the congeners present in penta-BDE-treated products from source-air-soil occurs with broadly similar efficiency, perhaps because there has been little weathering/degradation/alteration of the congener source pattern by processes operating during atmospheric transport or within the soil itself. BDE-183, a marker for the octa-BDE mix, was detected at concentrations ranging from <9 to 7000 (median approximately 50 ng kg(-1)). In most soils, it made a minor contribution to the sigma(ALL)PBDE concentration, but it was a major component in some samples from northern England. Forest soils tended to have higher concentrations than grasslands. Underlying the average soil composition, some differences in the congener pattern were observed. Notably, there was evidence of latitudinal fractionation, with the relative contribution of PBDE-47 and lighter congeners to the sigmaPBDE increasing northwards (with increasing distance from source areas), while the proportion of PBDE-99 and heavier congeners decreased. Plots of concentration against percentage soil organic matter had different slopes for different congeners. Higher slopes were generally seen for the lighter PBDEs (e.g., PBDE-47), indicating that they have undergone some air-surface exchange (hopping), while the slopes of heavier congeners (e.g., PBDE-153) were close to zero, indicating that they are retained more effectively by soils after deposition.

The global re-cycling of persistent organic pollutants is strongly retarded by soils.

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.