Excess of sulfate and dissolved inorganic carbon in groundwaters fueled by pyrite oxidation and organic matter loads – A multi-isotope approach

Author(s):  
Christoph Malik ◽  
Anna-K. Jenner ◽  
Iris Schmiedinger ◽  
Michael E. Böttcher

<p>The biogeochemistry of sulfur and carbon in groundwater of a Quaternary porous aquifer system and associated surface (lake) waters was investigated to identify processes of water mixing and the sources of dissolved sulfate and dissolved inorganic carbon (DIC). The study area is situated in North-Eastern Germany (Mecklenburg-Western Pomerania) close to the Baltic Sea coastline. The area is under impact by agricultural activity on a regional scale. A major goal was to identify the natural and anthropogenic key hydrobiogeochemical processes controlling the coupled element cycles upon groundwater development. Besides major and minor elements, redox-sensitive trace elements, nutrients, and stable mulit-isotope signatures (H, C, O, S) were considered.</p><p>While water isotopes of most groundwaters are positioned on the meteoric water line, surface waters are affected by an evaporation-induced enrichment of heavy isotopes. These shifts allow for a quantification of mixing proportions in influenced groundwater wells between direct precipitation-derived groundwater and  infiltrating lake water born fractions.</p><p>Major element hydrochemical and the carbon isotope composition of DIC indicate soil CO<sub>2</sub> and the subterrestrial dissolution of carbonate minerals within the aquifer matrix as primary sources for DIC. Furthermore, contributions from oxidized dissolved organic carbon (DOC) under water-saturated conditions are found.</p><p>The coupled sulfur and oxygen isotope composition of dissolved sulfate indicates an origin dominatly  from the subterrestrial oxidation of iron sulfides, mainly pyrite. These iron sulfides are found in the sediments making the modern porous aquifer, in the study area with a deduced sulfur isotope composition of about -12 per mil vs. VCDT. These findings coupled to enhanced loads in dissolved iron and manganese, but low nutrient concentrations indicate nitrate as an important driver for lithoautothrophic pyrite oxidation. At several sites, the enhanced sulfate loads led to dissimilatory sulfate reduction and, thereby, to in-situ transformation of DOC (and/or Methane) to DIC. The enhancements of sulfate and DIC seems to be a typical feature in North German younger groundwaters and strongly (in)directly impacted by anthropogenic forces.</p>

2015 ◽  
Vol 7 (1) ◽  
pp. 127-135 ◽  
Author(s):  
M. P. Humphreys ◽  
E. P. Achterberg ◽  
A. M. Griffiths ◽  
A. McDonald ◽  
A. J. Boyce

Abstract. The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in a batch process for 552 samples collected during two cruises in the northeastern Atlantic and Nordic Seas from June to August 2012. One cruise was part of the UK Ocean Acidification research programme, and the other was a repeat hydrographic transect of the Extended Ellett Line. In combination with measurements made of other variables on these and other cruises, these data can be used to constrain the anthropogenic component of dissolved inorganic carbon (DIC) in the interior ocean, and to help to determine the influence of biological carbon uptake on surface ocean carbonate chemistry. The measurements have been processed, quality-controlled and submitted to an in-preparation global compilation of seawater δ13CDIC data, and are available from the British Oceanographic Data Centre. The observed δ13CDIC values fall in a range from −0.58 to +2.37 ‰, relative to the Vienna Pee Dee Belemnite standard. The mean of the absolute differences between samples collected in duplicate in the same container type during both cruises and measured consecutively is 0.10 ‰, which corresponds to a 1σ uncertainty of 0.09 ‰, and which is within the range reported by other published studies of this kind. A crossover analysis was performed with nearby historical δ13CDIC data, indicating that any systematic offsets between our measurements and previously published results are negligible. Data doi:10.5285/09760a3a-c2b5-250b-e053-6c86abc037c0 (northeastern Atlantic), doi:10.5285/09511dd0-51db-0e21-e053-6c86abc09b95 (Nordic Seas).


2006 ◽  
Vol 6 (1-4) ◽  
pp. 53-59 ◽  
Author(s):  
Mariusz Orion-Jędrysek ◽  
Marta Kurasiewicz ◽  
Adriana Trojanowska ◽  
Dominika Lewicka ◽  
Agata Omilanowska ◽  
...  

2015 ◽  
Vol 8 (1) ◽  
pp. 57-82 ◽  
Author(s):  
M. P. Humphreys ◽  
E. P. Achterberg ◽  
A. M. Griffiths ◽  
A. McDonald ◽  
A. J. Boyce

Abstract. The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in samples collected during two cruises in the Northeastern Atlantic and Nordic Seas from June to August 2012. One cruise was part of the UK Ocean Acidification research programme, and the other was a repeat hydrographic transect of the Extended Ellett Line. In combination with measurements made of various other variables on these and other cruises, these data can be used to constrain the anthropogenic component of DIC in the interior ocean, and also assist in determining the influence of biological carbon uptake on surface ocean carbonate chemistry. The measurements have been processed, quality-controlled and submitted to an in-preparation global compilation of seawater δ13CDIC data, and are available from the British Oceanographic Data Centre. The observed δ13CDIC values fall in a range from −0.58 to +2.37‰, relative to the Vienna Peedee Belemnite standard. From duplicate samples collected during both cruises, the precision for the 552 results is 0.07‰, which is similar to other published studies of this kind. Data doi:10.5285/09760a3a-c2b5-250b-e053-6c86abc037c0 (Northeastern Atlantic), doi:10.5285/09511dd0-51db-0e21-e053-6c86abc09b95 (Nordic Seas).


Agronomy ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 403 ◽  
Author(s):  
Estibaliz Leibar-Porcel ◽  
Martin R. McAinsh ◽  
Ian C. Dodd

Enhancing root-zone (RZ) dissolved inorganic carbon (DIC) levels of plants grown hydroponically and aeroponically can increase biomass accumulation but may also alter plant nutrient uptake. These experiments investigated how bicarbonate (HCO3−) added to a hydroponic nutrient solution and CO2 gas added to an aeroponic system affected biomass and nutrient concentrations of lettuce and pepper plants. Applying high RZ HCO3− concentrations (20 mM) to lettuce plants grown hydroponically decreased foliar N, P, Cu, K, Mn and Zn concentrations, concurrent with decreased biomass accumulation (50% less than control plants). On the contrary, 1 mM RZ HCO3− promoted biomass accumulation (10% more than control plants), but this could not be attributed to higher tissue nutrient concentrations. While elevated RZ CO2 did not alter biomass accumulation and nutrient concentrations in pepper grown aeroponically, it decreased foliar Mg and S concentrations in lettuce grown aeroponically even though nutrient contents (concentration x biomass) did not differ between treatments, due to 22% more biomass than control plants. In addition, elevated RZ CO2 enhanced N, P, Cu and Zn contents relative to control plants, indicating greater uptake of those elements. Nevertheless, there was no consistent relationship between plant growth promotion and altered plant nutrition, suggesting alternative mechanisms of growth regulation.


2016 ◽  
Vol 8 (1) ◽  
pp. 221-233 ◽  
Author(s):  
Matthew P. Humphreys ◽  
Florence M. Greatrix ◽  
Eithne Tynan ◽  
Eric P. Achterberg ◽  
Alex M. Griffiths ◽  
...  

Abstract. The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in samples collected during June–July 2014 in the subpolar North Atlantic. Sample collection was carried out on the RRS James Clark Ross cruise JR302, part of the “Radiatively Active Gases from the North Atlantic Region and Climate Change” (RAGNARoCC) research programme. The observed δ13CDIC values for cruise JR302 fall in a range from −0.07 to +1.95 ‰, relative to the Vienna Pee Dee Belemnite standard. From duplicate samples collected during the cruise, the 1σ precision for the 341 results is 0.08 ‰, which is similar to our previous work and other studies of this kind. We also performed a cross-over analysis using nearby historical δ13CDIC data, which indicated that there were no significant systematic offsets between our measurements and previously published results. We also included seawater reference material (RM) produced by A. G. Dickson (Scripps Institution of Oceanography, USA) in every batch of analysis, enabling us to improve upon the calibration and quality-control procedures from a previous study. The δ13CDIC is consistent within each RM batch, although its value is not certified. We report δ13CDIC values of 1.15 ± 0.03 ‰ and 1.27 ± 0.05 ‰ for batches 141 and 144 respectively. Our JR302 δ13CDIC data can be used – along with measurements of other biogeochemical variables – to constrain the processes that control DIC in the interior ocean, in particular the oceanic uptake of anthropogenic carbon dioxide and the biological carbon pump. Our δ13CDIC results are available from the British Oceanographic Data Centre – doi:10.5285/22235f1a-b7f3-687f-e053-6c86abc0c8a6.


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