Short-term seawater inundation induces metal mobilisation in freshwater and acid sulfate soil environments.

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.

A simple and rapid ICP-MS/MS determination of sulfur isotope ratios (34S/32S) in complex natural waters: A new tool for tracing seawater intrusion in coastal systems.

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.

APC loss in breast cancer leads to doxorubicin resistance via STAT3 activation.

Resistance to chemotherapy is one of the leading causes of death from breast cancer. We recently established that loss of Adenomatous Polyposis Coli (APC) in the Mouse Mammary Tumor Virus - Polyoma middle T (MMTV-PyMT) transgenic mouse model results in resistance to cisplatin or doxorubicin-induced apoptosis. Herein, we aim to establish the mechanism that is responsible for APC-mediated chemotherapeutic resistance. Our data demonstrate that MMTV-PyMT;ApcMin/+ cells have increased signal transducer and activator of transcription 3 (STAT3) activation. STAT3 can be constitutively activated in breast cancer, maintains the tumor initiating cell (TIC) population, and upregulates multidrug resistance protein 1 (MDR1). The activation of STAT3 in the MMTV-PyMT;ApcMin/+ model is independent of interleukin 6 (IL-6); however, enhanced EGFR expression in the MMTV-PyMT;ApcMin/+ cells may be responsible for the increased STAT3 activation. Inhibiting STAT3 with a small molecule inhibitor A69 in combination with doxorubicin, but not cisplatin, restores drug sensitivity. A69 also decreases doxorubicin enhanced MDR1 gene expression and the TIC population enhanced by loss of APC. In summary, these results have revealed the molecular mechanisms of APC loss in breast cancer that can guide future treatment plans to counteract chemotherapeutic resistance.

Near shore groundwater acidification during and after a hydrological drought in the Lower Lakes, South Australia.

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.

Acidification of floodplains due to river level decline during drought.

A severe drought from 2007 to 2010 resulted in the lowest river levels (1.75 m decline from average) in over 90 years 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 (1-1.5 m) 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 3300 ha 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 (0.0026 tonnes acidity/ha/day) than in the irrigation (spring-summer) season (0.0013 tonnes acidity/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.

Changes in acidity and metal geochemistry in soils, groundwater, drain and river water in the Lower Murray River after a severe drought.

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 2 year period. The oxidation of an estimated 3500 ha 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 0.2 mol H(+)/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 pH 4.3, Fe, Al, Mn of 0.04-0.52 mmol/L) was observed at the same depths as the acidic soil layers. Nearly all of the dissolved Fe in the groundwater was present as Fe(2+). 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 (>3 years) following a return to pre-drought water levels.