Carbon dioxide and ocean acidification observations in UK waters. Synthesis report with a focus on 2010–2015

Key messages: 1.1 The process of ocean acidification is now relatively well-documented at the global scale as a long-term trend in the open ocean. However, short-term and spatial variability can be high. 1.2 New datasets made available since Charting Progress 2 make it possible to greatly improve the characterisation of CO2 and ocean acidification in UK waters. 3.1 Recent UK cruise data contribute to large gaps in national and global datasets. 3.2 The new UK measurements confirm that pH is highly variable, therefore it is important to measure consistently to determine any long term trends. 3.3 Over the past 30 years, North Sea pH has decreased at 0.0035±0.0014 pH units per year. 3.4 Upper ocean pH values are highest in spring, lowest in autumn. These changes reflect the seasonal cycles in photosynthesis, respiration (decomposition) and water mixing. 3.5 Carbonate saturation states are minimal in the winter, and lower in 7 more northerly, colder waters. This temperature-dependence could have implications for future warming of the seas. 3.6 Over the annual cycle, North-west European seas are net sinks of CO2. However, during late summer to autumn months, some coastal waters may be significant sources. 3.7 In seasonally-stratified waters, sea-floor organisms naturally experience lower pH and saturation states; they may therefore be more vulnerable to threshold changes. 3.8 Large pH changes (0.5 - 1.0 units) can occur in the top 1 cm of sediment; however, such effects are not well-documented. 3.9 A coupled forecast model estimates the decrease in pH trend within the North Sea to be -0.0036±0.00034 pH units per year, under a high greenhouse gas emissions scenario (RCP 8.5). 3.10 Seasonal estimates from the forecast model demonstrate areas of the North Sea that are particularly vulnerable to aragonite undersaturation

The Croker Carbonate Slabs: extensive methane-derived authigenic carbonate in the Irish Sea— nature, origin, longevity and environmental significance

The Croker Carbonate Slabs, in the UK sector of the Irish Sea, has shallow (70 to 100 m) water, strong (> 2 knot) tidal currents, coarse mobile surficial sediments and the most extensive methane-derived authigenic carbonate (MDAC) known in European waters. Multi-disciplinary studies (2004 to 2015) were commissioned specifically to document the benthic habitat, and have resulted in the designation of this site as a Marine Protected Area (MPA) under the European Commission’s Habitats Directive as an example of “Submarine structures formed by leaking gases”. However, this paper is focussed on the geoscience aspects of the site: the mineralogy and isotopic composition of the MDAC, its formation and age. It considers the implications of these findings with respect to the timing of the deglaciation of the area since the Last Glacial Maximum (LGM), and the environmental implications of the seepage of methane from the site over a period of at least 17,000 years. Carbon isotope ratios (δ13 C − 34 to − 54‰) confirm that the carbonate minerals (high-Mg calcite and aragonite) result from the anaerobic oxidation of methane. Widespread shallow gas within post-glacial sediments is sourced from underlying coal-bearing Carboniferous strata. Geophysical (side-scan sonar and multi-beam echo sounder) and visual surveys show that the MDAC occurs as isolated lumps, continuous pavements, and cliffs < 6 m tall, which post-date the post-glacial sediments, but are in places covered by a veneer of coarse mobile surficial sediments. U-Th dates (17,000 ± 5500 to 4000 ± 200 BP) suggest continual MDAC formation since the last glacial maximum, and constrain the postglacial sea level rise in this part of the Irish Sea; the site must have been submarine before MDAC formation started, whether or not methane was escaping. Visual and acoustic evidence of gas seepage is limited, but methane concentrations in the water are high (< 21.4 nmol l−1) and suggest present-day export to the atmosphere. It is also implied that significant methane release to the atmosphere occurred immediately after the retreat of the ice that covered the site during the LGM until 21.9 to 20.7 ka BP

The application of Diffusive Gradients in Thin Films (DGT) for improved understanding of metal behaviour at marine disposal sites

Assessment of the effects of sediment metal contamination on biological assemblages and function remains a key question in marine management, especially in relation to disposal activities. However, the appropriate description of bioavailable metal concentrations within pore-waters has rarely been reported. Here, metal behaviour and availability at contaminated dredged material disposal sites within UK waters were investigated using Diffusive Gradient in Thin films (DGT). Three stations, representing contrasting history and presence of dredge disposal were studied. Depth profiles of five metals were derived using DGT probes as well as discrete analysis of total metal concentrations from sliced cores. The metals analysed were: iron and manganese, both relevant to sediment biogeochemistry; cadmium, nickel and lead, classified as priority pollutants. DGT time-integrated labile flux profiles of the metals display behaviour consistent with increasingly reduced conditions at depth and availability to DGT (iron and manganese), subsurface peaks and a potential sedimentary source to the water column related to the disposal activity (lead and nickel) and release to pore-water linked to decomposition of enriched phytodetritus (cadmium). DGT data has the potential to improve our current understanding of metal behaviour at impacted sites and is suitable as a monitoring tool. DGT data can provide information on metal availability and fluxes within the sediment at high depth-resolution (5 mm steps). Differences observed in the resulting profiles between DGT and conventional total metal analysis illustrates the significance of considering both total metals and a potentially labile fraction. The study outcomes can help to inform and improve future disposal site impact assessment, and could be complemented with techniques such as Sediment Profile Imagery for improved biologically relevance, spatial coverage and cost-effective monitoring and sampling of dredge material disposal sites. Additionally, the application of this technology could help improve correlative work on biological impacts under national and international auspices when linking biological effects to more biologically relevant metal concentrations