A majority of the global net primary production of mangroves is unaccounted for by current carbon budgets. It has been hypothesized that this ''missing carbon'' is exported as dissolved inorganic carbon (DIC) from subsurface respiration and groundwater (or pore-water) exchange driven by tidal pumping. We tested this hypothesis by measuring concentrations and d 13 C values of DIC, dissolved organic carbon (DOC), and particulate organic carbon (POC), along with radon ( 222 Rn, a natural submarine groundwater discharge tracer), in a tidal creek in Moreton Bay, Australia. Concentrations and d 13 C values displayed consistent tidal variations, and mirrored the trend in 222 Rn in summer and winter. DIC and DOC were exported from, and POC was imported to, the mangroves during all tidal cycles. The exported DOC had a similar d 13 C value in summer and winter (, 230%). The exported d 13 C-DIC showed no difference between summer and winter and had a d 13 C value slightly more enriched (, 222.5%) than the exported DOC. The imported POC had differing values in summer (, 216%) and winter (, 222%), reflecting a combination of seagrass and estuarine particulate organic matter (POM) in summer and most likely a dominance of estuarine POM in winter. A coupled 222 Rn and carbon model showed that 93-99% of the DIC and 89-92% of the DOC exports were driven by groundwater advection. DIC export averaged 3 g C m 22 d 21 and was an order of magnitude higher than DOC export, and similar to global estimates of the mangrove missing carbon (i.e., , 1.9-2.7 g C m 22 d 21 ).
This paper investigates the natural and anthropogenic processes controlling sediment chemistry in Admiralty Bay, King George Island, Antarctica, emphasizing the area affected by the Brazilian Antarctic Station Comandante Ferraz (Ferraz). Total and bioavailable concentrations of sixteen elements were determined in 32 sediment and 14 soils samples. Factor analysis allowed us to distinguish three groups of samples: (1) Ferraz sediments, with higher content of total trace metals and organic matter; (2) control sediments, with intermediate characteristics; (3) Ferraz soils, with higher bioavailability of most metals due to its oxidizing condition and low organic matter content. Major elements such as Fe, Al, Ca and Ti presented similar levels in all three groups. Enrichment factor calculations showed that paints, sewage and petroleum contamination enhanced metal concentrations in Ferraz surface sediments as follows: B, Mo, and Pb (>90%); V and Zn (70-80%); Ni, Cu, Mg, and Mn (30-40%). Despite evidence of contamination in these sediments, the low bioavailability, probably caused by iron-sulfide, indicates small environmental risks.
Mangrove forests are hot spots in the global carbon cycle, yet the fate for a majority of mangrove net primary production remains unaccounted for. The relative proportions of alkalinity and dissolved CO 2 [CO 2 *] within the dissolved inorganic carbon (DIC) exported from mangroves is unknown, and therefore, the effect of mangrove DIC exports on coastal acidification remains unconstrained. Here we measured dissolved inorganic carbon parameters over complete tidal and diel cycles in six pristine mangrove tidal creeks covering a 26°latitudinal gradient in Australia and calculated the exchange of DIC, alkalinity, and [CO 2 *] between mangroves and the coastal ocean. We found a mean DIC export of 59 mmol m À2 d À1 across the six systems, ranging from import of 97 mmol m À2 d À1 to an export of 85 mmol m À2 d À1 . If the Australian transect is representative of global mangroves, upscaling our estimates would result in global DIC exports of 3.6 ± 1.1 Tmol C yr À1 , which accounts for approximately one third of the previously unaccounted for mangrove carbon sink. Alkalinity exchange ranged between an import of 1.2 mmol m À2 d À1 and an export of 117 mmol m À2 d À1 with an estimated global export of 4.2 ± 1.3 Tmol yr À1 . A net import of free CO 2 was estimated (À11.4 ± 14.8 mmol m À2 d À1 ) and was equivalent to approximately one third of the air-water CO 2 flux (33.1 ± 6.3 mmol m À2 d À1 ). Overall, the effect of DIC and alkalinity exports created a measurable localized increase in coastal ocean pH. Therefore, mangroves may partially counteract coastal acidification in adjacent tropical waters.
Worldwide, coral reef ecosystems are experiencing increasing pressure from a variety of anthropogenic perturbations including ocean warming and acidification, increased sedimentation, eutrophication, and overfishing, which could shift reefs to a condition of net calcium carbonate (CaCO3) dissolution and erosion. Herein, we determine the net calcification potential and the relative balance of net organic carbon metabolism (net community production; NCP) and net inorganic carbon metabolism (net community calcification; NCC) within 23 coral reef locations across the globe. In light of these results, we consider the suitability of using these two metrics developed from total alkalinity (TA) and dissolved inorganic carbon (DIC) measurements collected on different spatiotemporal scales to monitor coral reef biogeochemistry under anthropogenic change. All reefs in this study were net calcifying for the majority of observations as inferred from alkalinity depletion relative to offshore, although occasional observations of net dissolution occurred at most locations. However, reefs with lower net calcification potential (i.e., lower TA depletion) could shift towards net dissolution sooner than reefs with a higher potential. The percent influence of organic carbon fluxes on total changes in dissolved inorganic carbon (DIC) (i.e., NCP compared to the sum of NCP and NCC) ranged from 32% to 88% and reflected inherent biogeochemical differences between reefs. Reefs with the largest relative percentage of NCP experienced the largest variability in seawater pH for a given change in DIC, which is directly related to the reefs ability to elevate or suppress local pH relative to the open ocean. This work highlights the value of measuring coral reef carbonate chemistry when evaluating their susceptibility to ongoing global environmental change and offers a baseline from which to guide future conservation efforts aimed at preserving these valuable ecosystems.
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