Size Fractionation of Dissolved Organic Nitrogen in Peatland Fluvial Systems.

Understanding the nature and fate of nitrogen (N) in freshwater systems is crucial for assessing the risk of eutrophication. However, there is a paucity of information on the characterization of fluvial N in upland peat-dominated environments. Here, we employ a combination of field sampling and tangential flow ultrafiltration (TFU) to investigate the concentrations and fluxes of low molecular weight (LMW) and high molecular weight (HMW) dissolved organic N (DON) in a peatland stream-reservoir system in the south Pennines (UK). Our TFU results show that ∼26% of DON concentration is LMW DON and represents an estimated fluvial flux of 3.07 ± 22 kg N ha-1 during the study period. Our mass balance results reveal that the reservoir retains 71% of LMW DON input, which accounts for ∼25% retention of bioavailable (dissolved inorganic N + LMW DON) N. Our study suggests that current understanding of inorganic N as the sole source of bioavailable N with eutrophic significance in upland freshwaters requires a reappraisal. Evaluation of ecosystem response to increased loading of N needs to include a consideration of LMW DON.

Ingestion of Microplastics by Freshwater Tubifex Worms.

Microplastic contamination of the aquatic environment is a global issue. Microplastics can be ingested by organisms leading to negative physiological impacts. The ingestion of microplastics by freshwater invertebrates has not been reported outside the laboratory. Here we demonstrate the ingestion of microplastic particles by Tubifex tubifex from bottom sediments in a major urban waterbody fed by the River Irwell, Manchester, UK. The host sediments had microplastic concentrations ranging from 56 to 2543 particles kg-1. 87% of the Tubifex-ingested microplastic particles were microfibers (55-4100 µm in length), while the remaining 13% were microplastic fragments (50-4500 µm in length). FT-IR analysis revealed ingestion of a range of polymers, including polyester and acrylic fibers. While microbeads were present in the host sediment matrix, they were not detected in Tubifex worm tissue. The mean concentration of ingested microplastics was 129 ± 65.4 particles g-1 tissue. We also show that Tubifex worms retain microplastics for longer than they retain other particulate components of the ingested sediment matrix. Microplastic ingestion by Tubifex worms poses a significant risk for trophic transfer and biomagnification of microplastics up the aquatic food chain.

Peat Bogs as Hotspots for Organoarsenical Formation and Persistence.

Peatlands have received significant atmospheric inputs of As and S since the onset of the Industrial Revolution, but the effect of S deposition on the fate of As is largely unknown. It may encompass the formation of As sulfides and organosulfur-bound As, or the indirect stimulation of As biotransformation processes, which are presently not considered as important As immobilization pathways in wetlands. To investigate the immobilization mechanisms of anthropogenically derived As in peatlands subjected to long-term atmospheric pollution, we explored the solid-phase speciation of As, Fe, and S in English peat bogs by X-ray absorption spectroscopy. Additionally, we analyzed the speciation of As in pore- and streamwaters. Linear combination fits of extended X-ray absorption fine structure (EXAFS) data imply that 62-100% (average: 82%) of solid-phase As (Astot: 9-92 mg/kg) was present as organic As(V) and As(III). In agreement with appreciable concentrations of organoarsenicals in surface waters (pH: 4.0-4.4, Eh: 165-190 mV, average Astot: 1.5-129 µg/L), our findings reveal extensive biotransformation of atmospheric As and the enrichment of organoarsenicals in the peat, suggesting that the importance of organometal(loid)s in wetlands subjected to prolonged air pollution is higher than previously assumed.

Storage and behavior of As, Sb, Pb, and Cu in ombrotrophic peat bogs under contrasting water table conditions.

Concentration depth profiles and inventories of solid-phase As, Sb, Pb, and Cu were determined in ²¹°Pb-dated cores from an ombrotrophic peat bog in northwest England. Cores were collected from the peat dome and adjacent to an eroding gully. Down-core distributions of As, Sb, Pb, and Cu in the dome core are almost identical. The water table is close to the dome surface with only short-term draw-down. Under these conditions, As, Sb, Pb, and Cu are immobile, allowing the reconstruction of trends in historical contaminant deposition. The peak in atmospheric deposition of As, Sb, Pb, and Cu (4.59, 2.78, 147, and 26.7 mg m⁻² y⁻¹, respectively) occurred during the late 19th century. Stable Pb isotope ratios reveal that Pb deposition during this period was from indigenous and foreign sources. The mean water table is much lower at the gully edge, and there are pronounced interannual fluctuations. These conditions have not affected the integrity of the Pb and Cu records but have caused postdepositional mobilization and redistribution of As and Sb. Cumulative inventories show significant loss of As and Sb at the gully edge site. Long-term water table draw-down in ombrotrophic peat bogs has the potential to alter the geochemistry and fate of previously deposited As and Sb.

Seafloor microplastic hotspots controlled by deep-sea circulation.

Although microplastics are known to pervade the global seafloor, the processes that control their dispersal and concentration in the deep sea remain largely unknown. Here, we show that thermohaline-driven currents, which build extensive seafloor sediment accumulations, can control the distribution of microplastics and create hotspots with the highest concentrations reported for any seafloor setting (190 pieces per 50 grams). Previous studies propose that microplastics are transported to the seafloor by vertical settling from surface accumulations; here, we demonstrate that the spatial distribution and ultimate fate of microplastics are strongly controlled by near-bed thermohaline currents (bottom currents). These currents are known to supply oxygen and nutrients to deep-sea benthos, suggesting that deep-sea biodiversity hotspots are also likely to be microplastic hotspots.

Mobilisation of sediment-associated metals from historical Pb working sites on the River Sheaf, Sheffield, UK.

Spatial and temporal patterns of metal mobilisation from former water-powered, Pb working sites in a suburban area of Sheffield (UK) were investigated. Twelve time-integrated mass flux samplers were strategically deployed over two contrasting campaign periods (summer and winter). Suspended sediment samples were characterised magnetically and subjected to metal analysis. Metal levels in the upper River Sheaf showed a marked spatial and temporal variability. Pb concentrations in particular were relatively high (maximum 2132 mg kg(-1)). Their distribution tended to reflect the historical contamination of the valley by 17th to 19th century industry, especially during summer high discharge conditions. The mean suspended sediment Pb concentration (803 mg kg(-1)) exceeds contamination guidelines. It is unclear whether ground remediation of one of the seven floodplain sites in the catchment has been successful. The river is still affected by the legacy of at least two other Pb working sites.

Peat soils as a source of lead contamination to upland fluvial systems.

Upland peat soils are generally regarded as effective sinks of atmospherically deposited lead. However, the physical process of erosion has the potential to transform peat soils from sinks to sources of lead contamination. Lead input and fluvial lead outputs (dissolved+particulate) were estimated for a contaminated and severely eroding peatland catchment in the southern Pennines, UK. Lead input to the catchment is 30.0+/-6.0gha(-1)a(-1) and the output from the catchment is 317+/-22.4gha(-1)a(-1). Suspended particulate matter accounts for 85% of lead export. Contaminated peat soils of the catchment are a significant source of lead to the fluvial system. This study has demonstrated strong coupling between the physical process of erosion and the mobilization of lead into the fluvial system. The process of peat erosion should therefore be considered when estimating lead outputs from peatland catchments, especially in the context of climate change.

Scale-dependent spatial variability in peatland lead pollution in the southern Pennines, UK.

Increasingly, within-site and regional comparisons of peatland lead pollution have been undertaken using the inventory approach. The peatlands of the Peak District, southern Pennines, UK, have received significant atmospheric inputs of lead over the last few hundred years. A multi-core study at three peatland sites in the Peak District demonstrates significant within-site spatial variability in industrial lead pollution. Stochastic simulations reveal that 15 peat cores are required to calculate reliable lead inventories at the within-site and within-region scale for this highly polluted area of the southern Pennines. Within-site variability in lead pollution is dominant at the within-region scale. The study demonstrates that significant errors may be associated with peatland lead inventories at sites where only a single peat core has been used to calculate an inventory. Meaningful comparisons of lead inventories at the regional or global scale can only be made if the within-site variability of lead pollution has been quantified reliably.

Contrasting controls on arsenic and lead budgets for a degraded peatland catchment in Northern England.

Atmospheric deposition of trace metals and metalloids from anthropogenic sources has led to the contamination of many European peatlands. To assess the fate and behaviour of previously deposited arsenic and lead, we constructed catchment-scale mass budgets for a degraded peatland in Northern England. Our results show a large net export of both lead and arsenic via runoff (282 ± 21.3 gPb ha(-1) y(-1) and 60.4 ± 10.5 gAs ha(-1) y(-1)), but contrasting controls on this release. Suspended particulates account for the majority of lead export, whereas the aqueous phase dominates arsenic export. Lead release is driven by geomorphological processes and is a primary effect of erosion. Arsenic release is driven by the formation of a redox-dynamic zone in the peat associated with water table drawdown, a secondary effect of gully erosion. Degradation of peatland environments by natural and anthropogenic processes has the potential to release the accumulated pool of legacy contaminants to surface waters.

A classification and regression tree model of controls on dissolved inorganic nitrogen leaching from European forests.

Often, there is a non-linear relationship between atmospheric dissolved inorganic nitrogen (DIN) input and DIN leaching that is poorly captured by existing models. We present the first application of the non-parametric classification and regression tree approach to evaluate the key environmental drivers controlling DIN leaching from European forests. DIN leaching was classified as low (<3), medium (3-15) or high (>15kg N ha(-1) year(-1)) at 215 sites across Europe. The analysis identified throughfall NO(3)(-) deposition, acid deposition, hydrology, soil type, the carbon content of the soil, and the legacy of historic N deposition as the dominant drivers of DIN leaching for these forests. Ninety four percent of sites were successfully classified into the appropriate leaching category. This approach shows promise for understanding complex ecosystem responses to a wide range of anthropogenic stressors as well as an improved method for identifying risk and targeting pollution mitigation strategies in forest ecosystems.