Groundwater or floodwater? Assessing the pathways of metal exports from a coastal acid sulfate soil catchment

Daily observations of dissolved aluminum, iron, and manganese in an estuary downstream of a coastal acid sulfate soil (CASS) catchment provided insights into how floods and submarine groundwater discharge drive wetland metal exports. Extremely high Al, Fe, and Mn concentrations (up to 40, 374, and 8 mg L–1, respectively) were found in shallow acidic groundwaters from the Tuckean Swamp, Australia. Significant correlations between radon (a natural groundwater tracer) and metals in surface waters revealed that metal loads were driven primarily by groundwater discharge. Dissolved Fe, Mn, and Al loads during a 16-day flood triggered by a 213 mm rain event were respectively 80, 35, and 14% of the total surface water exports during the four months of observations. Counter clockwise hysteresis was observed for Fe and Mn in surface waters during the flood due to delayed groundwater inputs. Groundwater-derived Fe fluxes into artificial drains were 1 order of magnitude higher than total surface water exports, which is consistent with the known accumulation of monosulfidic black ooze within the wetland drains. Upscaling the Tuckean catchment export estimates yielded dissolved Fe fluxes from global acid sulfate soil catchments on the same order of magnitude of global river inputs into estuaries

Linking groundwater discharge to severe estuarine acidification during a flood in a modified wetland

Periodic acidification of waterways adjacent to coastal acid sulfate soils (CASS) is a significant land and water management issue in the subtropics. In this study, we use 5-months of continuous radon (222Rn, a natural groundwater tracer) observations to link estuarine acidification to groundwater discharge in an Australian CASS catchment (Tuckean Swamp). The radon time series began in the dry season, when radon activities were low (2−3 dpm L−1), and the pH of surface water was 6.4. We captured a major rain event (213 mm on 2 March 2010) that flooded the catchment. An immediate drop in pH during the flood may be attributed to surface water interactions with soil products. During the post-flood stage, increased radon activities (up to 19.3 dpm L−1) and floodplain groundwater discharge rates (up to 2.01 m3 s−1, equivalent to 19% of total runoff) coincided with low pH (3.77). Another spike in radon activities (13.2 dpm L−1) coincided with the lowest recorded surface water pH (3.62) after 72 mm of rain between 17 and 20 April 2010. About 80% of catchment acid exports occurred when the estuary was dominated by groundwater discharging from highly permeable CASS during the flood recession

Groundwater or Floodwater? Assessing the Pathways of Metal Exports from a Coastal Acid Sulfate Soil Catchment

Daily observations of dissolved aluminum, iron, and manganese in an estuary downstream of a coastal acid sulfate soil (CASS) catchment provided insights into how floods and submarine groundwater discharge drive wetland metal exports. Extremely high Al, Fe, and Mn concentrations (up to 40, 374, and 8 mg L^–1, respectively) were found in shallow acidic groundwaters from the Tuckean Swamp, Australia. Significant correlations between radon (a natural groundwater tracer) and metals in surface waters revealed that metal loads were driven primarily by groundwater discharge. Dissolved Fe, Mn, and Al loads during a 16-day flood triggered by a 213 mm rain event were respectively 80, 35, and 14% of the total surface water exports during the four months of observations. Counter clockwise hysteresis was observed for Fe and Mn in surface waters during the flood due to delayed groundwater inputs. Groundwater-derived Fe fluxes into artificial drains were 1 order of magnitude higher than total surface water exports, which is consistent with the known accumulation of monosulfidic black ooze within the wetland drains. Upscaling the Tuckean catchment export estimates yielded dissolved Fe fluxes from global acid sulfate soil catchments on the same order of magnitude of global river inputs into estuaries

The “salt wedge pump”: convection-driven pore-water exchange as a source of dissolved organic and inorganic carbon and nitrogen to an estuary

Hypoxia and anoxia in coastal waters have typically been explained by the respiration of sinking organic matter associated with nutrient over-enrichment and phytoplankton blooms. Here, we assess whether submarine groundwater discharge and seawater recirculation in sediments can explain widespread chemical anomalies, including low dissolved oxygen, in salt wedge estuaries. We rely on high-resolution radon (a natural groundwater and pore-water tracer), and dissolved carbon concentrations and stable isotope observations in the Yarra River estuary in Melbourne, Australia. Radon was highly enriched within the salt wedge, demonstrating enhanced pore-water exchange at this area. We use the term “salt wedge pump” to describe convection-driven advective pore-water exchange at the sediment–water interface during the upstream propagation of the salt wedge. Radon-derived convection-driven pore-water exchange rates within the salt wedge were estimated at 2.8 cm d−1, a value equivalent to 2.4% of the total river freshwater runoff to the estuary. Pore-water exchange led to pulsed dissolved inorganic carbon (DIC) and ammonium fluxes ∼ 10-fold higher than measured diffusive fluxes. In contrast, diffusive sediment oxygen uptake was 5-fold higher than oxygen uptake related to advective pore-water exchange. Estimated fluxes, associated with the nonconservative DIC, δ13C-DIC, and ammonium behavior within the estuary support convective pore-water exchange as a major source of DIC and ammonium to the estuary, but not of dissolved organic carbon, nitrate, dissolved organic nitrogen, and anoxia. Accounting for seawater recirculation in sediments may help reconcile unbalanced carbon and nitrogen budgets in several coastal systems

The contribution of groundwater discharge to nutrient exports from a coastal catchment: post flood seepage increases estuarine N/P ratios

Four months of daily nutrient and radon (a natural groundwater tracer) observations at the outlet of a heavily drained coastal wetland illustrated how episodic floods and diffuse groundwater seepage influence the biogeochemistry of a sub-tropical estuary (Richmond River, New South Wales, Australia). Our observations downstream of the Tuckean Swamp (an acid sulphate soil floodplain) covered a dry stage, a flood triggered by a 213-mm rain event and a post-flood stage when surface water chemistry was dominated by groundwater discharge. Significant correlations were found between radon and ammonium and N/P ratios and between radon and dissolved organic nitrogen (DON) during the post-flood stage. While the flood lasted for 14 % of the time of the surface water time series, it accounted for 18 % of NH4, 32 % of NO x , 66 % of DON, 58 % of PO4 and 55 % of dissolved organic phosphorus (DOP) catchment exports. Over the 4-month study period, groundwater fluxes of 35.0, 3.6, 36.3, 0.5 and 0.7 mmol m−2 day−1 for NH4, NO x , DON, PO4 and DOP, respectively, were estimated. The groundwater contribution to the total surface water catchment exports was nearly 100 % for ammonium, and% for the other nutrients. Post-flood groundwater seepage shifted the system from a DON to a dissolved inorganic N-dominated system and doubled N/P ratios in surface waters. We hypothesise that the Richmond River Estuary N/P ratios may reflect a widespread trend of tidal rivers and estuaries becoming more groundwater-dominated and phosphorus-limited as coastal wetlands are drained for agriculture, grazing and development