『Abstract
Marine sediments are the main sink in the oceanic phosphorus
(P) cycle. The activity of benthic microorganisms is decisive
for regeneration, reflux, or burial of inorganic phosphate (Pi),
which has a strong impact on marine productivity. Recent formation
of phosphorites on the continental shelf and a succession of different
sedimentary environments make the Benguela upwelling system a
prime region for studying the role of microbes in P biogeochemistry.
The oxygen isotope signature of pore water phosphate (δ18OP) carries characteristic information of microbial
P cycling: Intracellular turnover of phosphorylated biomolecules
results in isotopic equilibrium with ambient water, while enzymatic
regeneration of Pi from organic matter produces distinct offsets
from equilibrium. The balance of these two processes is the major
control for δ18OP.
Our study assesses the importance of microbial P cycling relative
to regeneration of Pi from organic matter from a transect across
the Namibian continental shelf and slope by combining pore water
chemistry (sulfate, sulfide, ferrous iron, Pi), steady-state turnover
rate modeling, and oxygen isotope geochemistry of Pi.
We found δ18OP values in a range
from 12.8‰ to 26.6‰, both in equilibrium as well as pronounced
disequilibrium with water. Our data show a trend towards regeneration
signatures (disequilibrium) under low mineralization activity
and high Pi concentrations. These findings are opposite to observations
from water column studies where regeneration signatures were found
to coincide with high mineralization activity and high Pi concentrations.
It appears that preferential Pi regeneration in marine sediments
does not necessarily coincide with a disequilibrium δ18OP signature. We propose that microbial Pi uptake
strategies, which are controlled by Pi availability, are decisive
for the alteration of the isotope signature. This hypothesis is
supported by the observation of efficient microbial Pi turnover
(equilibrium signatures) in the phosphogenic sediments of the
Benguela upwelling system.』
1. Introduction
2. materials and methods
2.1. Region of the study
2.2. Retrieval of sediment cores and pore water sampling
2.3. Quantification of dissolved pore water compounds
2.4. Isotopic analysis of phosphate
2.4.1. Micro extraction of pore water phosphate and isotope
ratio mass spectrometry
2.4.2. Determination of water oxygen isotopes, calculation of
isotopic equilibrium and correction of δ18OP
2.5. Modeling of steady state production of dissolved inorganic
carbon and phosphate
2.6. The phosphate oxygen isotope balance of regeneration and
microbial turnover
2.6.1. Endmember 1: isotope equilibrium in microbial phosphate
metabolism
2.6.2. Endmember 2: kinetic fractionation and incorporation
of water-oxygen during extracellular phosphate regeneration from
organic matter
2.6.2.1. Consideration of substrate and enzyme systems for
calculation of the regeneration endmember
2.6.2.2. Composition of phosphorus bound to organic matter
2.6.3. Construction of the isotope mass balance model
2.6.3.1. The steady state mass balance of Pi in sediment porewater
2.6.3.2. Isotope mass balance model
3. Results
3.1. Pore water geochemistry
3.2. Dissolved inorganic carbon and phosphate turnover
3.3. Water and phosphate oxygen isotopes
4. Discussion
4.1. Key sources for pore water phosphate in the Benguela
upwelling system
4.1.1. Ferric oxyhydroxides as Pi source
4.1.2. Mineralization of organic matter and preferential regeneration
of Pi: relation to carbon-to-phosphorus ratios of organic matter
4.1.3. Role of advection and diffusion of Pi from above and
below
4.2. Classification of stations with similar geochemical setting
4.3. Comparison to results of the mass balance model: efficiency
of microbial phosphate cycling
4.3.1. Preservation of regeneration signature (disequilibrium)
at low activity, low Pi sites
4.3.2. Equilibrium signature at high activity, high Pi mudbelt
sites
4.3.3. Unequal display of slope sites with intermediate DIC
production
4.4. Apparent inconsistencies between geochemical data and oxygen
isotope mass balance regarding enhanced Pi regeneration
4.4.1. Microbial Pi transport systems: consequences for phosphate
isotope biosignatures
4.4.2. The mudbelt as a unique environment for marine P cycling
5. Conclusion
Acknowledgments
Appendix A. Supplementary data
References