The study encompasses three cases: a segment of the pristine carbonate aquifer with relatively low dissolved sulphate concentrations, often below 20 mg/L; a chalk aquifer contaminated by hydrocarbons, where microbial sulphate reduction was confirmed; and an experiment involving dissimilatory sulphate reduction. Bayesian models were developed using Python and its libraries, alongside the open-source probabilistic programming framework PYMC3, to assess the sulphate reduction hypothesis, ascertain the initial conditions of these processes, and demonstrate the applicability of this probabilistic method in elucidating hydrogeochemical processes, surpassing the widely used Rayleigh distillation model. The model produced robust and dependable results for both aquifer cases. Additionally, a model was devised to validate controllable and known conditions. The findings hold promise and may find relevance in similar hydrogeochemical processes. This study underscores the effectiveness of Bayesian modelling in revealing initial process conditions, particularly in situations where knowledge and data are limited. This limitation is often encountered with isotopic data, which remain relatively scarce due to the considerable effort required for material preparation and the costs associated with such investigations. Moreover, this study contributes to the identification of redox zonation, which holds significant implications for water quality-related concerns such as pollutant migration, remediation of hydrocarbon- contaminated sites, and meeting potable water quality standards regarding metal concentrations.

We identify a major sulfur isotope excursion in Eurasian faunal bone collagen from the last 50,000 years, here termed the Late Pleniglacial Sulfur Excursion. Our analysis suggests this is linked to changing permafrost conditions, presenting the utility of faunal collagen δ34S as a proxy for permafrost dynamics, a critical component of the global carbon cycle. Our findings complicate the use of archaeological faunal sulfur isotopes for mobility and palaeodietary studies. Sulfur isotope excursions in skeletal collagen samples from Eurasia suggest rapidly changing biogeochemical processes across the region from about 30,000 to 15,000 years ago, potentially related to changing permafrost conditions.

A plume-scale mass balance is developed to assess the natural attenuation (NA) of dissolved organic contaminants in fractured, dual-porosity aquifers. This methodology can be used to evaluate contaminant distribution within the aquifer, plume source term, contaminant biodegradation and plume status. The approach is illustrated for a site on the UK Upper Chalk aquifer impacted by petroleum fuel containing methyl tert -butyl ether (MTBE) and tert -amyl methyl ether (TAME). Variability in site investigation data and uncertainty in the mass balance were assessed using probabilistic analysis. The analysis shows that benzene, toluene, m/p-xylene and o-xylene (BTEX) compounds are biodegraded primarily by denitrification and sulfate reduction in the aquifer, with an equivalent plume-scale first-order biodegradation rate of 0.49 a −1 . Other biodegradation processes are less important. Sorption contributes to hydrocarbon attenuation in the aquifer but is less important for MTBE and TAME. Uncertainty in the plume source term and site hydrogeological parameters had the greatest effect on the mass balance. The probabilistic analysis enabled the most likely long-term composition of the plume source term to be deduced and provided a site-specific estimate of contaminant mass flux for the prediction of plume development. The mass balance methodology provides a novel approach to improve NA assessments for petroleum hydrocarbons and other organic contaminants in these aquifer settings. Supplementary material: Plume organic chemistry, aquifer hydraulic conductivity and probability distribution functions used for mass balance inputs are available at https://doi.org/10.6084/m9.figshare.c.7016429 Thematic collection: This article is part of the Monitoring the aquifers collection available at: https://www.lyellcollection.org/topic/collections/monitoring-the-aquifers

Groundwater flow and contaminant migration tracing is a vital method of identifying and characterising pollutant source-pathway-receptor linkages in karst aquifers. Bacteriophages are an attractive alternative tracer to non-reactive fluorescent dye tracers, as high titres (>1012 pfu mL−1) can be safely released into the aquifer, offering improved tracer detectability. However, the interpretation of bacteriophage tracer breakthrough curves is complicated as their fate and transport are impacted by aquifer physicochemical conditions. A comparative tracer migration experiment was conducted in a peri-urban catchment in southeast England to characterise the behaviour of MS2 bacteriophage relative to sodium fluorescein dye in a karstic chalk aquifer. Tracers were released into a stream sink and detected at two abstraction boreholes located 3 km and 10 km away. At both sites, the loss of MS2 phage greatly exceeded that of the solute tracer. In contrast, the qualitative shape of the dye and phage breakthrough curves were visually very similar, suggesting that the bacteriophage arriving at each site was governed by comparable transport parameters to the non-reactive dye tracer. The colloid filtration theory was applied to explain the apparent contradiction of comparable tracer breakthrough patterns despite massive phage losses in the subsurface. One-dimensional transport models were also fitted to each breakthrough curve to facilitate a quantitative comparison of the transport parameter values. The model results suggest that the bacteriophage migrates through the conduit system slightly faster than the fluorescent dye, but that the former is significantly less dispersed. These results suggest that whilst the bacteriophage tracer cannot be used to predict receptor concentrations from transport via karstic flow paths, it can provide estimates for groundwater flow and solute contaminant transit times. This study also provides insight into the attenuation and transport of pathogenic viruses in karstic chalk aquifers.

The Permo-Triassic mass extinction was linked to catastrophic environmental changes and large igneous province (LIP) volcanism. In addition to the widespread marine losses, the Permo-Triassic event was the most severe terrestrial ecological crisis in Earth's history and the only known mass extinction among insects, but the cause of extinction on land remains unclear. In this study, high-resolution Hg concentration records and multiple-archive S-isotope analyses of sediments from the Junggar Basin (China) provide evidence of repeated pulses of volcanic-S (acid rain) and increased Hg loading culminating in a crisis of terrestrial biota in the Junggar Basin coeval with the interval of LIP emplacement. Minor S-isotope analyses are, however, inconsistent with total ozone layer collapse. Our data suggest that LIP volcanism repeatedly stressed end-Permian terrestrial environments in the ~300 kyr preceding the marine extinction locally via S-driven acidification and deposition of Hg, and globally via pulsed addition of CO2.

The hydrology and biogeochemistry of perennial groundwater springs emerging in the forefields of retreating Svalbard glaciers are considered through a single-site, multi-year study at Foxfonna, and a multi-site spatial sampling programme during consecutive winter seasons. We show that such springs are commonplace in the forefields of retreating Svalbard glaciers, including even cold-based glaciers underlain by permafrost. The groundwaters all contain geogenic methane and are generally anoxic, but reveal a range of different redox en-vironments linked to sulfide oxidation, denitrification and sulfate reduction. The principal source waters for these springs seems to be snow and firn meltwaters entering bergschrund crevasses at high elevation glacier margins. At Foxfonna, the glacier's strongly negative mass balance and transition to cold-based thermal con-ditions have resulted in reduced groundwater discharge into the proglacial river due to lower rates of recharge (less dilution). Throughout these changes, sulfide oxidation coupled to Na-Silicate weathering has remained a dominant reaction, driving a three-fold increase in electrical conductivity since 2010. The period has also been characterised by the complete loss of NO3- since summer 2018, as well as short-lived changes in the Oxidation -Reduction Potential and methane concentration. Therefore, climate-driven glacial retreat influences both the quantity and quality of groundwaters entering downstream drainage systems, which exist in spite of cold-based glaciers and permafrost being prevalent in this part of the Arctic.

Iso-Wetlands is a new, NERC-funded collaborative research project involving researchers at UCL Institute of Archaeology, the University of Leeds and the UK Centre for Ecology and Hydrology. The project is developing sulfur isotope analysis of archaeological plants and animals as a new tool for exploring hydrological conditions under which agricultural production was taking place. This development has the potential to improve understanding of water management strategies in the past, particularly in relation to seasonal floodwater agriculture and wetland agriculture (for example, rice paddy systems). The project will open wider possibilities for the use of sulfur isotopes in archaeology and ecology to examine wetland habitat use by both people and animals.

Fractured carbonate aquifers derive their transmissivity essentially from a well-developed network of solutionally-enhanced fractures and conduits that can lead to high groundwater velocities and high vulnerability to contamination of water quality. Characterisation of the variation of hydraulic properties with depth is important for delineating source protection areas, characterising contaminant fate and transport, determination of the effectiveness of aquifer remediation, and parameter estimation for models. In this work, ambient open borehole uniform and point injection dilution tests were conducted on observation boreholes in the unconfined Cretaceous Chalk aquifer of East Yorkshire, UK, and interpreted in conjunction with other data via the implementation of a new work flow. This resulted in the characterisation of flow in these boreholes and the inference of properties such as groundwater flow patterns and velocities in the surrounding aquifer formation. Our workflow allowed sections of open boreholes showing horizontal versus vertical flow to be distinguished, and the magnitude of such flows and exchanges with the aquifer to be determined. Flow within boreholes were then used to characterise: i) presence and direction of vertical hydraulic gradients; ii) nature and depth distribution of flowing features; iii) depth interval porosity and permeability estimation of the flowing features from overall borehole transmissivity and geophysical image or caliper logs; iv) groundwater velocity estimation in the surrounding aquifer. Discrete flowing features were distributed across the range of depths sampled by the observation boreholes (typically up to 45-60 mbgl), but the majority were located in the zone of water table fluctuation marked by solutionally enlarged flow features. Quantitative interpretation of both uniform injection (tracer distributed throughout the open borehole section) and point injection (slug of tracer introduced at targeted depth) yielded vertical velocities within the borehole water column in broad agreement with those measured by flow logging. Depth specific fracture kinematic porosities inferred from the ambient dilution data combined with long-interval pump test and geophysical log data ranged between 3.7 x 10(-4)-4.1 x 10(-3) with an average of 2.1 x 10(-3); these values were in excellent agreement with those from other methods applied to the same aquifer such as larger scale pumping tests. A new approach to estimation of groundwater velocities from the dilution test data using externally measured hydraulic gradients gave inferred horizontal groundwater velocities ranging between 60 and 850 m/day, in full agreement with those from previously conducted borehole-to-borehole tracer tests. These results confirm that the studied aquifer is karstic, with rapid preferential pathways which have implication for flow and transport modelling, and pollution vulnerability. Our study results indicate that ambient single-borehole dilution approaches can provide an inexpensive and reliable approach for the characterisation of fractured and karstic aquifers.

Warming of ground is causing microbial decomposition of previously frozen sedimentary organic carbon in Arctic permafrost. However, the heterogeneity of the permafrost landscape and its hydrological processes result in different biogeochemical processes across relatively small scales, with implications for predicting the timing and magnitude of permafrost carbon emissions. The biogeochemical processes of iron- and sulfate-reduction produce carbon dioxide and suppress methanogenesis. Hence, in this study, the biogeochemical processes occurring in the active layer and permafrost of a high Arctic fjord valley in Svalbard are identified from the geochemical and stable isotope analysis of aqueous and particulate fractions in sediment cores collected from ice-wedge polygons with contrasting water content. In the drier polygons, only a small concentration of organic carbon (<5.40 dry weight%) has accumulated. Sediment cores from these drier polygons have aqueous and solid phase chemistries that imply sulfide oxidation coupled to carbonate and silicate dissolution, leading to high concentrations of aqueous iron and sulfate in the pore water profiles. These results are corroborated by delta S-34 and delta O-18 values of sulfate in active layer pore waters, which indicate the oxidative weathering of sedimentary pyrite utilising either oxygen or ferric iron as oxidising agents. Conversely, in the sediments of the consistently water-saturated polygons, which contain a high content of organic carbon (up to 45 dry weight%), the formation of pyrite and siderite occurred via the reduction of iron and sulfate. delta S-34 and delta O-18 values of sulfate in active layer pore waters from these water-saturated polygons display a strong positive correlation (R-2= 0.98), supporting the importance of sulfate reduction in removing sulfate from the pore water. The significant contrast in the dominant biogeochemical processes between the water-saturated and drier polygons indicates that small-scale hydrological variability between polygons induces large differences in the concentration of organic carbon and in the cycling of iron and sulfur, with ramifications for the decomposition pathway of organic carbon in permafrost environments.

The 13C signature is evaluated for various environmental compartments (vegetation, soils, soil gas, rock and groundwater) for three crystalline rock terrains in England and Norway. The data are used to evaluate the extent to which stable carbon isotopic data can be applied to deduce whether the alkalinity in crystalline bedrock groundwaters has its origin in hydrolysis of carbonate or silicate minerals by CO2. The resolution of this issue has profound implications for the role of weathering of crystalline rocks as a global sink for CO2. In the investigated English terrain (Isles of Scilly), groundwaters are hydrochemically immature and DIC is predominantly in the form of carbonic acid with a soil gas signature. In the Norwegian terrains, the evidence is not conclusive but is consistent with a significant fraction of the groundwater DIC being derived from silicate hydrolysis by CO2. A combined consideration of pH, alkalinity and carbon isotope data, plotted alongside theoretical evolutionary pathways on bivariate diagrams, strongly suggests real evolutionary pathways are likely to be hybrid, potentially involving both open and closed CO2 conditions.

The relationship between salt water and the strength of Chalk forming the coastal cliffs of northwest Europe was investigated. Uniaxial compressive strength (UCS) tests on core samples from three horizontal boreholes drilled at the base of Chalk cliffs in East Sussex, UK, showed the weakest Chalk to be near the cliff face. The UCS nearly doubled over the length of the 9 m deep boreholes. The UCS results were close to values expected for Chalk of this intact dry density for samples farthest from the cliff face. High chloride concentrations (salt water) of up to 69 000 mg/l were found to be associated with the lowest UCS values closest to the cliff face. Lower chloride concentrations, with values of 1850 mg/l or less and often with a non-marine origin, were found in the stronger core samples. It can be concluded that the Chalk coastal cliffs in the areas tested became weaker towards the cliff face. This can, in part, be linked to salt water weakening although it is likely that other factors are also contributing to this phenomenon.

The Cretaceous-Paleogene (K-Pg) mass extinction event 66 million years ago led to large changes to the global carbon cycle, primarily via a decrease in primary or export productivity of the oceans. However, the effects of this event and longer-term environmental changes during the Late Cretaceous on the global sulfur cycle are not well understood. We report new carbonate associated sulfate (CAS) sulfur isotope data derived from marine macrofossil shell material from a highly expanded high latitude Maastrichtian to Danian (69-65.5 Ma) succession located on Seymour Island, Antarctica. These data represent the highest resolution seawater sulfate record ever generated for this time interval, and are broadly in agreement with previous low-resolution estimates for the latest Cretaceous and Paleocene. A vigorous assessment of CAS preservation using sulfate oxygen, carbonate carbon and oxygen isotopes and trace element data, suggests factors affecting preservation of primary seawater CAS isotopes in ancient biogenic samples are complex, and not necessarily linked to the preservation of original carbonate mineralogy or chemistry. Primary data indicate a generally stable sulfur cycle in the early-mid Maastrichtian (69 Ma), with some fluctuations that could be related to increased pyrite burial during the 'mid-Maastrichtian Event'. This is followed by an enigmatic +4 parts per thousand increase in delta S-34(CAS) during the late Maastrichtian (68-66 Ma), culminating in a peak in values in the immediate aftermath of the K-Pg extinction which may be related to temporary development of oceanic anoxia in the aftermath of the Chicxulub bolide impact. There is no evidence of the direct influence of Deccan volcanism on the seawater sulfate isotopic record during the late Maastrichtian, nor of a direct influence by the Chicxulub impact itself. During the early Paleocene (magnetochron C29R) a prominent negative excursion in seawater delta(34) S of 3-4 parts per thousand suggests that a global decline in organic carbon burial related to collapse in export productivity, also impacted the sulfur cycle via a significant drop in pyrite burial. Box modelling suggests that to achieve an excursion of this magnitude, pyrite burial must be reduced by >15%, with a possible role for a short term increase in global weathering rates. Recovery of the sulfur cycle to pre-extinction values occurs at the same time (similar to 320 kyrs) as initial carbon cycle recovery globally. These recoveries are also contemporaneous with an initial increase in local alpha diversity of marine macrofossil faunas, suggesting biosphere-geosphere links during recovery from the mass extinction. Modelling further indicates that concentrations of sulfate in the oceans must have been 2 mM, lower than previous estimates for the Late Cretaceous and Paleocene and an order of magnitude lower than today. (C) 2018 The Authors. Published by Elsevier Ltd.

The majority of open-pit mineral workings are established in hydrogeological environments in which unsaturated drainage or saturated groundwater flow occurs predominantly via discrete fracture networks. Stress relaxation resulting from open-pit mineral extraction can lead to a change in host rock fracture network configuration and fracture hydraulic properties, with the potential to change local hydrogeological characteristics and groundwater flow regimes. Research being undertaken at the University of Leeds is applying a DFN approach to investigate the hydrogeological significance of such effects in relation to methodologies for impact assessment at mineral sites. The paper presents a summary of the research approach and preliminary results. A discrete finite element approach to geomechanical modelling has been undertaken with simulation of DFN evolution in response to lithostatic unloading for a range of pre-existing discontinuity configurations, lithological types and variations in in-situ stress regimes. Preliminary modelling results have provided improved understanding of the vertical and lateral extent of potential DFN response for a range of excavation profiles. Research results will be used to define conditions under which open-pit mineral extraction could lead to hydrogeologically significant change in fracture flow drainage characteristics at a scale relevant to hydrogeological impact assessment for new and existing mineral workings.

Various studies report substantial increases in intrinsic water-use efficiency (Wi), estimated using carbon isotopes in tree rings, suggesting trees are gaining increasingly more carbon per unit water lost due to increases in atmospheric CO2. Usually, reconstructions do not, however, correct for the effect of intrinsic developmental changes in Wi as trees grow larger. Here we show, by comparingWi across varying tree sizes at one CO2 level, that ignoring such developmental effects can severely affect inferences of trees' Wi. Wi doubled or even tripled over a trees' lifespan in three broadleaf species due to changes in tree height and light availability alone, and there are also weak trends for Pine trees. Developmental trends in broadleaf species are as large as the trends previously assigned to CO2 and climate. Credible future tree ring isotope studies require explicit accounting for species-specific developmental effects before CO2 and climate effects are inferred.

Identification of nitrogen (N) sources is important in water quality control and management. Nitrogen pollution can lead to eutrophication of waterbodies and high concentrations of nitrate in drinking water can pose potential health problems. The 15N isotope and nitrogen fluxes budget approach is useful for determining the source of NO3‐ to surface waters. In this study, mass balance and 15N isotope approaches and nitrogen flux budgets were applied to identify total nitrogen (TN) sources and nitrogen transformation processes in the Menlou Reservoir (MR), Jiaodong Peninsula, China. The different fractions of nitrogen and their 15N isotope signatures were analyzed in the reservoir water, river water, groundwater, soil, and atmospheric precipitation. The results indicate that surface runoff pollution (e.g., fertilizer and animal manure) is the main source of NO3‐ in MR. High concentrations of TN in MR are caused by low nitrogen self‐purification (denitrification) rate, low sediment adsorption capacity, and the influx of NO3‐ rich groundwater.

Geochemical cycling and biological toxicity of sulfur in marine sediments is closely related to the activity of organisms. This study investigated the distribution and potential impact on benthic environments of acid volatile sulfur (AVS), chromium(II)-reducible sulfur (CRS), elemental sulfur (ES), total S, C, N and Fe in superficial sediments across the Bohai Sea, Yellow Sea and East China Sea. The composition of reduced inorganic sulfur in the three study areas was dominated by CRS (averaging 72% of total reduced inorganic sulfur). The low AVS content (average of 1.12 μmol g(-1)) of the sediments and the low values of AVS/CRS (average 0.34 μmol g(-1)), degree of pyritization and degree of sulphidization indicate that there is sufficient available iron in the sediment to restrict the threat of sulphide toxicity to benthic organisms in most of the study areas. However, high organic matter loads in parts of the study areas have resulted in enhanced accumulation of AVS, resulting in a higher toxicity risk.

Understanding the geochemical cycling of sulfur in sediments is important because it can have implications for both modern environments (e.g., deterioration of water quality) and interpretation of the ancient past (e.g., sediment C/S ratios can be used as indicators of palaeodepositional environment). This study investigates the geochemical characteristics of sulfur, iron, and organic carbon in fluvial and coastal surface sediments of the Laizhou Bay region, China. A total of 63 sediment samples were taken across the whole Laizhou Bay marine region and the 14 major tidal rivers draining into it. Acid volatile sulfur, chromium (II)-reducible sulfur and elemental sulfur, total organic carbon, and total nitrogen were present in higher concentrations in the fluvial sediment than in the marine sediment of Laizhou Bay. The composition of reduced inorganic sulfur in surface sediments was dominated by acid volatile sulfur and chromium (II)-reducible sulfur. In fluvial sediments, sulfate reduction and formation of reduced inorganic sulfur were controlled by TOC and reactive iron synchronously. High C/S ratios in the marine sediments indicate that the diagenetic processes in Laizhou Bay have been affected by rapid deposition of sediment from the Yellow River in recent decades.

A tree ring oxygen isotope (δ18OTR) chronology developed from one species (Cedrela odorata) growing in a single site has been shown to be a sensitive proxy for rainfall over the Amazon Basin, thus allowing reconstructions of precipitation in a region where meteorological records are short and scarce. Although these results suggest that there should be large-scale (>100km) spatial coherence of δ18OTR records in the Amazon, this has not been tested. Furthermore, it is of interest to investigate whether other, possibly longer-lived, species similarly record interannual variation of Amazon precipitation, and can be used to develop climate sensitive isotope chronologies. In this study, we measured δ18O in tree rings from seven lowland and one highland tree species from Bolivia. We found that cross-dating with δ18OTR gave more accurate tree ring dates than using ring width. Our “isotope cross-dating approach” is confirmed with radiocarbon “bomb-peak” dates, and has the potential to greatly facilitate development of δ18OTR records in the tropics, identify dating errors, and check annual ring formation in tropical trees. Six of the seven lowland species correlated significantly with C. odorata, showing that variation in δ18OTR has a coherent imprint across very different species, most likely arising from a dominant influence of source water δ18O on δ18OTR. In addition we show that δ18OTR series cohere over large distances, within and between species. Comparison of two C. odorata δ18OTR chronologies from sites several hundreds of kilometres apart showed a very strong correlation (r=0.80, p<0.001, 1901–2001), and a significant (but weaker) relationship was found between lowland C. odorata trees and a Polylepis tarapacana tree growing in the distant Altiplano (r=0.39, p<0.01, 1931–2001). This large-scale coherence of δ18OTR records is probably triggered by a strong spatial coherence in precipitation δ18O due to large-scale controls. These results highlight the strength of δ18OTR as a precipitation proxy, and open the way for temporal and spatial expansion of precipitation reconstructions in South America.