This chapter provides an overview of near-surface geochemical processes operating on Earth, with special emphasis placed on (i) marine weathering such as alteration and dissolution of silicates, carbonates and terrigenous riverine particles in the ocean, complemented by (ii) reverse weathering reactions leading to marine authigenic clay formation, and the impact of these phenomena on ocean alkalinity budget and the chemical and isotope composition of seawater. Model simulations of the above processes provide estimates of the global marine fluxes of major cations (Na+, K+, Mg2+, Ca2+) and alkalinity in the ocean induced by silicate weathering and dissolution of terrigenous material in seawater. Additional constraints on silicate vs. carbonate weathering, oceanic/coastal CaCO3 cycling, and paleo-seawater reconstructions are provided via the stable and radiogenic isotope systems of alkali and alkaline earth metals (Li, K, Mg, Ca, and Sr isotopes) that are discussed within the context of marine and reverse weathering in the present and past ocean.

A likely consequence of sea level rise during the next century will be progressive inundation of seawater through the current unsaturated zone in coastal-margin soils. It is unclear how this will change the biogeochemical cycling of iron, sulfur and carbon over different time scales and soil types. A long-term (540 day) laboratory experiment, slowly inundating intact coastal soil cores with seawater from the ‘bottom up’, was conducted to observe how coupled iron and sulfur dynamics change in different soil types. Pore water was extracted from the 60 cm cores at 10 cm depth intervals every 90 days and analysed for pH, electrical conductivity (EC), Fe2+, HS− and dissolved metals (Fe, Mn, As, Cd, Cu, Ni, Pb, Co, Zn) as well as stable sulfur (34S/32S) and radiogenic strontium (87Sr/86Sr) isotopes. Destructive solid phase analyses (for reactive Fe, acid volatile and chromium reducible sulfur (AVS and CRS) and total organic carbon (TOC)) were made at the start and end of the experiment. Iron and sulfate reduction was induced in soils with readily available TOC as anoxic conditions established, evidenced by statistically significant increases (P < 0.001) in dissolved Fe2+ and sulfide concentrations in porewaters, as well as simultaneous and progressive increase in the sulfur isotope (34S/32S) ratios. An increase in AVS indicated formation of metastable iron sulfide (FeS) minerals resulting from Fe2+ and sulfide in porewaters post inundation. This was supported by PHREEQC modelling of local mineral saturation states/indices in the system. Overall, the Fe2+ concentration increased to a peak at between 270 and 360 days, and then began decreasing at some depths, indicating slowing iron reduction, presumably because reactive iron (oxyhydro)oxides became progressively consumed by microbially driven reductive processes. However, microbially mediated sulfate reduction continued as abundant sulfate was still available from seawater. In the absence of free Fe2+, sulfide accumulated in the porewater, but only in those soils inundated the longest (>360 days), and with greater than 5% TOC. The combined use of sulfur (34S/32S) and strontium (87Sr/86Sr) isotopes supported the observed results, and represents a new and robust technique to quantify progressive sulfate reduction and seawater mixing phenomena in coastal soils. This study gives new insights into the biogeochemical cycling of sulfur and iron in soils experiencing seawater inundation from sea level rise over longer timescales. It is likely that sulfidisation (due to in-situ sulfate reduction) will begin to affect coastal wetland soils, especially in areas where TOC is high and where reactive iron depletes over time. This has potential consequences for sulfide toxicity in coastal soils and environments globally.

Climate change is leading to global sea level rise. Storm surges and higher tides will generate short-term 'pulses' of seawater into freshwater systems, often for the first time in over 3000 years. The effect of increased seawater inundation upon soil geochemistry is poorly understood. We identified 12 sites in South Australia which are predicted to be inundated by seawater storm surges in the next 20 years. Within these 12 sites are three distinct environments; fresh water streams and lakes, hypersaline saltmarsh and mangroves, and acid sulfate soils. Soils were inundated with seawater under laboratory conditions to replicate a short-term (two weeks) inundation by a storm surge. Lowering of redox potential and dissolution of high concentrations of reactive Mn and Fe in freshwater environments lead to the release of dissolved Fe and Mn in the soils from freshwater environments. Soils also released As, Cu, Ni, Cd and Co, while Zn and Pb were less mobilised. Concentrations of metals released exceeded water quality guidelines to protect freshwater aquatic ecosystems in most cases. By comparison, hypersaline soils only released minor amounts of Mn, Fe, Cd and Ni, and only in some of the soils. The moderately acidic acid sulfate soil (pH 5.41) reductively dissolved Mn and Fe releasing significant amount of Fe and Mn as well as As, Cu, Ni, Cd and Co, whereas almost all metal species decreased in the porewaters of the strongly acidic acid sulfate soil (pH 2.77). The response to short-term seawater inundation in acid sulfate soils was dependent upon the baseline soil acidification status. This study highlights the need for further research on seawater inundation of coastal soils as sea levels rise and storm surges penetrate further inland.

Introduction: scenario-based thinking for resilient coastal landscapesCoastal landscapes are under threat globally due to climate change, in particular due to rapidly rising sea levels ( IPCC, 2021).These dynamic coastal environments are valuable for a range of land uses including tidal and supratidal ecosystems, human settlement, agriculture and various built infrastructures ( Small & Nicholls, 2003).Together these land uses form what we call herein " anthropogenic coastal landscapes".In describing them in this way, we acknowledge that there is a continuum of more natural and more built or artificial conditions ( Hobbs, Higgs, & Hall, 2013;Hobbs et al., 2014;Lundholm, 2015;Sutton-Grier, Wowk, & Bamford, 2015;Mangone, 2016).The anthropogenic coastline has been formed through a complex combination of processes.For instance, artificial or grey infrastructure has often been designed to arrest or defend against geomorphological change to prioritize land uses such as housing and agriculture yet coastlines keep evolving regardless with landscape types such as beaches and wetlands in a continual state of flux.In many coastal suburbs, infrastructure, such as stormwater systems, housing and coastal wall defenses, have become defunct through climaterelated forces including sea level rise, tidal flooding, saltwater intrusion through and across built infrastructures and storm surges.As a consequence, we need to consider how to address climate change threats.The most immediate and obvious approach to defending built and settlement assets is a linear, defensive approach epitomized by dikes and seawalls.However, this can have disastrous outcomes for all land uses, even those which are intended to be protected ( Zevenbergen, Rijke, Van Herk, & Bloemen, 2015).An ultimately more powerful approach is through adaptation and making space for the integration of various natural and 15

Conventional sulfur isotope measurements in complex natural liquid or solid samples via GS-IRMS are complicated, time consuming and relatively expensive. Here we assessed a novel 'collision cell' based ICP-MS/MS approach which can determine the sulfur isotope abundances (i.e., 34S/32S ratios, expressed as δ34S) in complex coastal waters rapidly, accurately and with minimal sample preparation. The approach was validated via repeated ICP-MS/MS measurement of S isotope certified reference materials (CRM) providing accurate and reproducible results, with a typical uncertainty on δ34S of around 1.1-1.5‰ (1SD). This novel approach is suitable for water samples with sulfur concentrations at or above 2 μg/mL (ppm). Matrix matching between samples and the CRM was necessary when seawater-like solutions were analysed addressing common matrix related errors. The ICP-MS/MS approach was used to investigate δ34S signature of porewaters from a variety of coastal systems in South Australia (including acid sulfate soils), and how they responded to progressive seawater inundation. Importantly, inundation induced a shift in S isotope ratio in affected porewaters in which δ34S approached that of seawater. The simple sample preparation, with rapid and accurate δ34S determination of complex natural waters using the ICP MS/MS approach, greatly increases the applicability of sulfur isotope tracing studies to identify and monitor sources and bio-geochemical pathways of S in coastal and near-surface environments.

An extreme hydrological drought in the Lower Lakes of the Murray-Darling Basin (Ramsar listed site) resulted in exposure of large areas of lake bed (25% of pre-drought lake area), containing the reduced iron (Fe) sulfide mineral pyrite. The pyrite oxidised and the resulting acidification (pH<4) posed risks of acid and metals entering shallow groundwater and potentially discharging to the remaining lake water body. Piezometer transects were installed at four locations and monitoring of the groundwater levels and quality was undertaken for six years from 2009 (drought) to 2014 (4years post-reinundation). Acidic (pH3-5) groundwater was recorded at three of the four piezometer locations and included sites close to the lake water. The acidic groundwater (0.5-2m below lake bed) at these sites is likely to have originated from the transport of acid from the upper oxidised sediment layer formed during the drought. High soluble metal (Fe, Al, Mn) levels were also recorded at acidic locations. Acidic shallow groundwater has persisted at many sites for over 4years following reinundation post-drought, and is likely due to slow diffusion and limited sulfate reduction. Increases in dissolved Fe and Mn with decreases in redox potential suggest that reductive dissolution of Fe and Mn hydrous oxides and Fe oxy-hydroxysulfate minerals (e.g. jarosite) occurred post-drought. Groundwater hydraulic head gradients were low, indicating there was limited potential for groundwater to discharge to the lake. The hydraulic gradients at all locations were dynamic with complex relationships along the near-shore environment. The results highlight the long lasting and severe effects on groundwater that can occur following hydrological drought in aquatic environments with sulfidic sediments.

Acid sulfate soils with sulfuric material (pH<4) can have significant impacts on surface water quality and aquatic ecosystems due to low pH and high soluble metal concentrations in runoff and drainage discharges. There has been limited research on the complex geochemical transformations that occur along flow pathways from the soil acidity source to receiving waters. We studied the integrated geochemistry of metals in acid sulfate soils with sulfuric material, groundwater, drain and river water in the Lower Murray River (South Australia) over a 2year period. The oxidation of an estimated 3500ha of acid sulfate soils with sulfidic material (pH>4) underlying this former floodplain occurred due to falling river and groundwater levels during the 2006–2010 extreme “millennium” drought. A low pH (<4.5) soil layer was found approximately 1–2.5m below ground level with substantial amounts (up to 0.2molH+/kg dry weight) of available/soluble acidity and retained acidity in the form of the Fe oxyhydroxy sulfate mineral jarosite. The jarosite appears to be dissolving over time and buffering the sub-surface soil layers at pH≈4. Metal (Fe, Al, Mn) and metalloid (As) lability was greatly increased in the acidic soil layer. Highly acidic and metal rich groundwater (median pH4.3, Fe, Al, Mn of 0.04–0.52mmol/L) was observed at the same depths as the acidic soil layers. Nearly all of the dissolved Fe in the groundwater was present as Fe2+. In the drains, increases in pH and redox potential promoted formation of the Fe oxyhydroxysulfate mineral schwertmannite. This mineral precipitation transferred a portion of the dissolved acidity to the drain sediments. Upon discharge to, and dilution of, the acid drainage in the river, pH neutralisation and rapid oxidation, hydrolysis, and precipitation of solid Al and Fe phases occurred in a localised area. Acidity is persisting (>3years) following a return to pre-drought water levels.

A severe drought from 2007 to 2010 resulted in the lowest river levels (1.75m decline from average) in over 90years of records at the end of the Murray–Darling Basin in South Australia. Due to the low river level and inability to apply irrigation, the groundwater depth on the adjacent agricultural flood plain also declined substantially (1–1.5m) and the alluvial clay subsoils dried and cracked. Sulfidic material (pH>4, predominantly in the form of pyrite, FeS2) in these subsoils oxidised to form sulfuric material (pH<4) over an estimated 3300ha on 13 floodplains. Much of the acidity in the deeply cracked contaminated soil layers was in available form (in pore water and on cation exchange sites), with some layers having retained acidity (iron oxyhydroxysulfate mineral jarosite). Post drought, the rapid raising of surface and ground water levels mobilised acidity in acid sulfate soil profiles to the floodplain drainage channels and this was transported back to the river via pumping. The drainage water exhibited low pH (2–5) with high soluble metal (Al, Co, Mn, Fe, Mn, Ni, and Zn) concentrations, in exceedance of guidelines for ecosystem protection. Irrigation increased the short-term transport of acidity, however loads were generally greater in the non-irrigation (winter) season when rainfall is highest (0.0026tonnesacidity/ha/day) than in the irrigation (spring–summer) season (0.0013tonnesacidity/ha/day). Measured reductions in groundwater acidity and increases in pH have been observed over time but severe acidification persisted in floodplain sediments and waters for over two years post-drought. Results from 2-dimensional modelling of the river-floodplain hydrological processes were consistent with field measurements during the drying phase and illustrated how the declining river levels led to floodplain acidification. A modelled management scenario demonstrated how river level stabilisation and limited irrigation could have prevented, or greatly lessened the severity of the acidification.

The impact of extreme low flows on the water quality of the Lower Murray River and Lower Lakes (Alexandrina and Albert) in South Australia was assessed by comparing water quality from five sites during an extreme low flow period (March 2007–November 2009) and a preceding reference period (March 2003–November 2005). Significant increases in salinity, total nitrogen, total phosphorus, chlorophyll a and turbidity were observed in the Lower Lakes during the low flow period. Consequently, water quality guidelines for the protection of aquatic ecosystems were greatly exceeded. Principal Component Analysis, empirical and mass balance model calculations suggested these changes could be attributed primarily to the lack of flushing resulting in concentration of dissolved and suspended material in the lakes, and increased sediment resuspension as the lakes became shallower. The river sites also showed significant but more minor salinity increases during the extreme low flow period, but nutrient and turbidity concentrations decreased. The most plausible reasons for these changes were decreased catchment inputs and increased influence of saline groundwater inputs. The results highlight the vulnerability of arid and semi-arid lake systems to reduced flow conditions as a result of climatic changes and/or water management decisions.

Bombah Broadwater is a shallow coastal lake within the Ramsar-listed Myall Lakes system on the mid-north coast of New South Wales, Australia. Increased nutrient and sediment loads resulting from catchment modification are thought to have instigated the loss of aquatic plants in the lake, causing it to “switch” from a clear, macrophyte dominated system (similar to the conditions in present day Myall Lake) to a turbid, phytoplankton dominated system. To assess this hypothesis, charophytes, foraminifera and aquatic fauna remains from an 800 year sediment record were examined. The sediment chronology was established using 14C, 210Pb and 137Cs radiometric dating and sediment composition. Interestingly, a clear increase in charophytes since European arrival conflicted with the hypothesised aquatic plant loss. Hence, it appears Bombah Broadwater has not undergone a change in stable state since European arrival. An additional and unexpected finding in the patterns of the foraminifera and testate amoeba suggest that Bombah Broadwater has freshened substantially since European arrival. This freshening may have resulted from increased catchment run off as a result of the clearance of catchment vegetation. Since catchment vegetation clearance is widespread in Australia, this finding raises the possibility that post-settlement freshening of coastal lakes may be a common occurrence.