Air pollutant contamination and acidification of surface waters in the North York Moors, UK: Multi-proxy evidence from the sediments of a moorland pool

Despite the extensive geographical range of palaeolimnological studies designed to assess the extent of surface water acidification in the United Kingdom during the 1980s, little attention was paid to the status of surface waters in the North York Moors (NYM). In this paper, we present sediment core data from a moorland pool in the NYM that provide a record of air pollution contamination and surface water acidification. The 41-cm-long core was divided into three lithostratigraphic units. The lower two comprise peaty soils and peats, respectively, that date to between approximately 8080 and 6740 cal. BP. The uppermost unit comprises peaty lake muds dating from between approximately ad 1790 and the present day (ad 2006). The lower two units contain pollen dominated by forest taxa, whereas the uppermost unit contains pollen indicative of open landscape conditions similar to those of the present. Heavy metal, spheroidal carbonaceous particle, mineral magnetics and stable isotope analysis of the upper sediments show clear evidence of contamination by air pollutants derived from fossil-fuel combustion over the last c. 150years, and diatom analysis indicates that the naturally acidic pool became more acidic during the 20th century. We conclude that the exceptionally acidic surface waters of the pool at present (pH=c. 4.1) are the result of a long history of air pollution and not because of naturally acidic local conditions. We argue that the highly acidic surface waters elsewhere in the NYM are similarly acidified and that the lack of evidence of significant recovery from acidification, despite major reductions in the emissions of acidic gases that have taken place over the last c. 30years, indicates the continuing influence of pollutant sulphur stored in catchment peats, a legacy of over 150years of acid deposition.

In situ, high-resolution imaging of labile phosphorus in sediments of a large eutrophic lake

Understanding the labile status of phosphorus (P) in sediments is crucial for managing a eutrophic lake, but it is hindered by lacking in situ data particularly on a catchment scale. In this study, we for the first time characterized in situ labile P in sediments with the Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique at a two-dimensional (2D), submillimeter resolution in a large eutrophic lake (Lake Taihu, China, with an area of 2338km²). The concentration of DGT-labile P in the sediment profiles showed strong variation mostly ranging from 0.01 to 0.35mgL^-1 with a considerable number of hotspots. The horizontal heterogeneity index of labile P varied from 0.04 to 4.5. High values appeared at the depths of 0-30mm, likely reflecting an active layer of labile P under the sediment-water interface (SWI). Concentration gradients of labile P were observed from the high-resolution 1D DGT profiles in both the sediment and overlying water layers close to the SWI. The apparent diffusion flux of P across the SWI was calculated between -21 and 65ngcm^-2d^-1, which showed that the sediments tended to be a source and sink of overlying water P in the algal- and macrophyte-dominated regions, respectively. The DGT-labile P in the 0-30mm active layer showed a better correlation with overlying water P than the labile P measured by ex situ chemical extraction methods. It implies that in situ, high-resolution profiling of labile P with DGT is a more reliable approach and will significantly extend our ability in in situ monitoring of the labile status of P in sediments in the field.

Distal tephrochronology in volcanic regions: Challenges and insights from Kamchatkan lake sediments

Kamchatka is one of the world’s most active volcanic regions and has hosted many explosive eruptions during the Holocene. These eruptions had the potential to disperse tephra over wide areas, forming time-synchronous markers wherever those tephras are found. Recent research in Kamchatka has begun to focus on the geochemical analysis of individual glass shards in order to characterise tephra layers. We have applied this approach to the study of visible tephras from three lakes – one in central and two in northern Kamchatka – with the aim of identifying key tephras and potential issues in the application of distal (>100 km from an active volcano) tephra in volcanically complex regions. In total, 23 tephras from 22 tephra beds have been geochemically analysed, representing products from at least four volcanic systems in Kamchatka. We demonstrate that distal lake sediments in the region can yield reliable tephrostratigraphies, capturing tephra from eruptions that have the greatest potential to disperse volcanic ash beyond the region. We draw attention to issues relating to correlating and distinguishing key marker horizons from the highly active Shiveluch Volcano, namely the need to ensure inter-lab comparability of geochemical data and good chronological control of the proximal and distal tephras. Importantly, we have also extended the known distribution of two key tephra isochrons from the Ksudach volcano. Our work contributes valuable glass geochemical on data several key marker beds that will facilitate future tephra and palaeoenvironmental research within and beyond Kamchatka.

Holocene climate and environmental change in north-eastern Kamchatka (Russian Far East), inferred from a multi-proxy study of lake sediments

A sediment record from a small lake in the north-eastern part of the Kamchatka Peninsula has been investigated in a multi-proxy study to gain knowledge of Holocene climatic and environmental change. Pollen, diatoms, chironomids and selected geochemical parameters were analysed and the sediment record was dated with radiocarbon. The study shows Holocene changes in the terrestrial vegetation as well as responses of the lake ecosystem to catchment maturity and multiple stressors, such as climate change and volcanic eruptions. Climate change is the major driving force resulting in the recorded environmental changes in the lake, although recurrent tephra deposition events also contributed. The sediment record has an age at the base of about 10,000 cal yrs BP, and during the first 400 years the climate was cold and the lake exhibited extensive ice-cover during winter and relatively low primary production. Soils in the catchment were poor with shrub alder and birches dominating the vegetation surrounding the lake. At about 9600–8900 cal yrs BP the climate was cold and moist, and strong seasonal wind stress resulted in reduced ice-cover and increased primary production. After ca. 8900 cal yrs BP the forest density increased around the lake, runoff decreased in a generally drier climate resulting in decreased primary production in the lake until ca. 7000 cal yrs BP. This generally dry climate was interrupted by a brief climatic perturbation, possibly attributed to the 8.2 ka event, indicating increasingly windy conditions with thick snow cover, reduced ice-cover and slightly elevated primary production in the lake. The diatom record shows maximum thermal stratification at ca. 6300–5800 cal yrs BP and indicates together with the geochemical proxies a dry and slightly warmer climate resulting in a high productive lake. The most remarkably change in the catchment vegetation occurred at ca. 4200 cal yrs BP in the form of a conspicuous increase in Siberian dwarf pine (Pinus pumila), indicating a shift to a cooler climate with a thicker and more long-lasting snow cover. This vegetational change was accompanied by marked shifts in the diatom and chironomid stratigraphies, which are also indicative of colder climate and more extensive ice-cover.

Balancing the (carbon) budget: Using linear inverse models to estimate carbon flows and mass-balance 13C:15N labelling experiments in low oxygen sediments.

Over 1 million km² of seafloor experience permanent low-oxygen conditions within oxygen minimum zones (OMZs). OMZs are predicted to grow as a consequence of climate change, potentially affecting oceanic biogeochemical cycles. The Arabian Sea OMZ impinges upon the western Indian continental margin at bathyal depths (150 - 1500 m) producing a strong depth dependent oxygen gradient at the sea floor. The influence of the OMZ upon the short term processing of organic matter by sediment ecosystems was investigated using in situ stable isotope pulse chase experiments. These deployed doses of ¹³C:¹⁵N labeled organic matter onto the sediment surface at four stations from across the OMZ (water depth 540 - 1100 m; [O₂] = 0.35 - 15 μM). In order to prevent experimentally anoxia, the mesocosms were not sealed. ¹³C and ¹⁵N labels were traced into sediment, bacteria, fauna and ¹³C into sediment porewater DIC and DOC. However, the DIC and DOC flux to the water column could not be measured, limiting our capacity to obtain mass-balance for C in each experimental mesocosm. Linear Inverse Modeling (LIM) provides a method to obtain a mass-balanced model of carbon flow that integrates stable-isotope tracer data with community biomass and biogeochemical flux data from a range of sources. Here we present an adaptation of the LIM methodology used to investigate how ecosystem structure influenced carbon flow across the Indian margin OMZ. We demonstrate how oxygen conditions affect food-web complexity, affecting the linkages between the bacteria, foraminifera and metazoan fauna, and their contributions to benthic respiration. The food-web models demonstrate how changes in ecosystem complexity are associated with oxygen availability across the OMZ and allow us to obtain a complete carbon budget for the stationa where stable-isotope labelling experiments were conducted.

Novel precipitated zirconia-based DGT technique for high-resolution imaging of oxyanions in waters and sediments

Water-sediment exchange is a fundamental component of oxyanion cycling in the environment. Yet, many of the (im)mobilization processes overlay complex spatial and temporal redox regimes that occur within millimeters of the interface. Only a few methods exist that can reliably capture these porewater fluxes, with the most popular being high-resolution diffusive gradients in thin films (HR-DGT). However, functionality of HR-DGT is restricted by the availability of suitable analyte binding agents within the sampler, which must be simple to cast and homogeneously distributed in the binding layer, exhibit adequate sorption capacities, be resistive to chemical change, and possess a very fine particle size (≤10 μm). A novel binding layer was synthesized to meet these requirements by in situ precipitation of zirconia into a precast hydrogel. The particle diameter ≤0.2 μm of zirconia in this precipitated gel was uniform and at least 50-times smaller than the conventional molding approach. Further, this gel had superior binding and stability characteristics compared with the commonly used ferrihydrite HR-DGT technique and could be easily fabricated as an ultrathin gel (60 μm) for simultaneous oxygen imaging in conjunction with planar-optodes. Chemical imaging of anion and oxygen fluxes using the new sampler were evaluated on Lake Taihu sediments.

Novel DGT method with tri-metal oxide adsorbent for in situ spatiotemporal flux measurement of fluoride in waters and sediments

Natural mineral-water interface reactions drive ecosystem/global fluoride (F−) cycling. These small-scale processes prove challenging to monitoring due to mobilization being highly localized and variable; influenced by changing climate, hydrology, dissolution chemistries and pedogenosis. These release events could be captured in situ by the passive sampling technique, diffusive gradients in thin-films (DGT), providing a cost-effective and time-integrated measurement of F− mobilization. However, attempts to develop the method for F− have been unsuccessful due to the very restrictive operational ranges that most F−-absorbents function within. A new hybrid-DGT technique for F− quantification containing a three-phase fine particle composite (Fesingle bondAlsingle bondCe, FAC) adsorbent was developed and evaluated. Sampler response was validated in laboratory and field deployments, passing solution chemistry QC within ionic strength and pH ranges of 0–200 mmol L−1 and 4.3–9.1, respectively, and exhibiting high sorption capacities (98 ± 8 μg cm−2). FAC-DGT measurements adequately predicted up to weeklong averaged in situ F− fluvial fluxes in a freshwater river and F− concentrations in a wastewater treatment flume determined by high frequency active sampling. While, millimetre-scale diffusive fluxes across the sediment-water interface were modeled for three contrasting lake bed sediments from a F−-enriched lake using the new FAC-DGT platform.

High Resolution measurement and mapping of tungstate in waters, soils and sediments using the low-disturbance DGT sampling technique.

Increasing tungsten (W) use for industrial and military applications has resulted in greater W discharge into natural waters, soils and sediments. Risk modeling of W transport and fate in the environment relies on measurement of the release/mobilization flux of W in the bulk media and the interfaces between matrix compartments. Diffusive gradients in thin-films (DGT) is a promising passive sampling technique to acquire such information. DGT devices equipped with the newly developed high-resolution binding gels (precipitated zirconia, PZ, or ferrihydrite, PF, gels) or classic/conventional ferrihydrite slurry gel were comprehensively assessed for measuring W in waters. FerrihydriteDGT can measure W at various ionic strengths (0.001–0.5 mol L−1 NaNO3) and pH (4–8), while PZDGT can operate across slightly wider environmental conditions. The three DGT configurations gave comparable results for soil W measurement, showing that typically W resupply is relatively poorly sustained. 1D and 2D high-resolution W profiling across sediment—water and hotspot—bulk media interfaces from Lake Taihu were obtained using PZDGT coupled with laser ablation ICP–MS measurement, and the apparent diffusion fluxes across the interfaces were calculated using a numerical model.