Carbon dioxide concentrations for the Last Millennium, Antarctica

The most direct method of investigating past variations of the atmospheric CO2 concentration before 1958, when continuous direct atmospheric CO2 measurements started, is the analysis of air extracted from suitable ice cores. Here we present a new detailed CO2 record from the Dronning Maud Land (DML) ice core, drilled in the framework of the European Project for Ice Coring in Antarctica (EPICA) and some new measurements on a previously drilled ice core from the South Pole. The DML CO2 record shows an increase from about 278 to 282 parts per million by volume (ppmv) between ad 1000 and ad 1200 and a fairly continuous decrease to a mean value of about 277 ppmv around ad 1700. While the new South Pole measurements agree well with DML at the minimum at ad 1700 they are on average about 2 ppmv lower during the period ad 1000-1500. Published measurements from the coastal high-accumulation site Law Dome are considered as very reliable because of the reproducibility of the measurements, high temporal resolution and an accurate time scale. Other Antarctic ice cores could not, or only partly, reproduce the pre-industrial measurements from Law Dome. A comparison of the trends of DML and Law Dome shows a general agreement. However we should be able to rule out co-variations caused by the same artefact. Two possible effects are discussed, first production of CO2 by chemical reactions and second diffusion of dissolved air through the ice matrix into the bubbles. While the first effect cannot be totally excluded, comparison of the Law Dome and DML record shows that dissolved air diffusing to bubbles cannot be responsible for the pre-industrial variation. Therefore, the new record is not a proof of the Law Dome results but the first very strong support from an ice core of the Antarctic plateau.

Hexachlorocyclohexanes concentration in air and ocean water

Hexachlorocyclohexanes (HCHs) are ubiquitous organic pollutants derived from pesticide application. They are subject to long-range transport, persistent in the environment, and capable of accumulation in biota. Shipboard measurements of HCH isomers (a-, b- and g-HCH) in surface seawater and boundary layer atmospheric samples were conducted in the Atlantic and the Southern Ocean in October to December of 2008. SumHCHs concentrations (the sum of a-, g- and b-HCH) in the lower atmosphere ranged from 12 to 37 pg/m**3 (mean: 27 ± 11 pg/m**3) in the Northern Hemisphere (NH), and from 1.5 to 4.0 pg/m**3 (mean: 2.8 ± 1.1 pg/m**3) in the Southern Hemisphere (SH), respectively. Water concentrations were: a-HCH 0.33-47 pg/l, g-HCH 0.02-33 pg/l and b-HCH 0.11-9.5 pg/l. Dissolved HCH concentrations decreased from the North Atlantic to the Southern Ocean, indicating historical use of HCHs in the NH. Spatial distribution showed increasing concentrations from the equator towards North and South latitudes illustrating the concept of cold trapping in high latitudes and less interhemispheric mixing process. In comparison to concentrations measured in 1987-1999/2000, gaseous HCHs were slightly lower, while dissolved HCHs decreased by factor of 2-3 orders of magnitude. Air-water exchange gradients suggested net deposition for a-HCH (mean: 3800 pg/m**2/day) and g-HCH (mean: 2000 pg/m**2/day), whereas b-HCH varied between equilibrium (volatilization: <0-12 pg/m**2/day) and net deposition (range: 6-690 pg/m**2/day). Climate change may significantly accelerate the release of "old" HCHs from continental storage (e.g. soil, vegetation and high mountains) and drive long-range transport from sources to deposition in the open oceans. Biological productivities may interfere with the air-water exchange process as well. Consequently, further investigation is necessary to elucidate the long term trends and the biogeochemical turnover of HCHs in the oceanic environment.

Chemical characterization of dissolved organic compounds from coastal sea surface microlayers (Baltic Sea, Germany)

The physicochemical properties of the sea surface microlayer (SML), i.e. the boundary layer between the air and the sea, and its impact on air-sea exchange processes have been investigated for decades. However, a detailed description about these processes remains incomplete. In order to obtain a better chemical characterization of the SML, in a case study three pairs of SML and corresponding bulk water samples were taken in the southern Baltic Sea. The samples were analyzed for dissolved organic carbon and dissolved total nitrogen, as well as for several organic nitrogen containing compounds and carbohydrates, namely aliphatic amines, dissolved free amino acids, dissolved free monosaccharides, sugar alcohols, and monosaccharide anhydrates. Therefore, reasonable analytical procedures with respect to desalting and enrichment were established. All aliphatic amines and the majority of the investigated amino acids (11 out of 18) were found in the samples with average concentrations between 53 ng/l and 1574 ng/l. The concentrations of carbohydrates were slightly higher, averaging 2900 ng/l. Calculation of the enrichment factor (EF) between the sea surface microlayer and the bulk water showed that dissolved total nitrogen was more enriched (EF: 1.1 and 1.2) in the SML than dissolved organic carbon (EF: 1.0 and 1.1). The nitrogen containing organic compounds were generally found to be enriched in the SML (EF: 1.9-9.2), whereas dissolved carbohydrates were not enriched or even depleted (EF: 0.7-1.2). Although the investigated compounds contributed on average only 0.3% to the dissolved organic carbon and 0.4% to the total dissolved nitrogen fraction, these results underline the importance of single compound analysis to determine SML structure, function, and its potential for a transfer of compounds into the atmosphere.

Impacts of elevated CO2 on particulate and dissolved organic matter production: microcosm experiments using iron-deficient plankton communities in open subarctic waters

Response of phytoplankton to increasing CO2 in seawater in terms of physiology and ecology is key to predicting changes in marine ecosystems. However, responses of natural plankton communities especially in the open ocean to higher CO2 levels have not been fully examined. We conducted CO2 manipulation experiments in the Bering Sea and the central subarctic Pacific, known as high nutrient and low chlorophyll regions, in summer 2007 to investigate the response of organic matter production in iron-deficient plankton communities to CO2 increases. During the 14-day incubations of surface waters with natural plankton assemblages in microcosms under multiple pCO2 levels, the dynamics of particulate organic carbon (POC) and nitrogen (PN), and dissolved organic carbon (DOC) and phosphorus (DOP) were examined with the plankton community compositions. In the Bering site, net production of POC, PN, and DOP relative to net chlorophyll-a production decreased with increasing pCO2. While net produced POC:PN did not show any CO2-related variations, net produced DOC:DOP increased with increasing pCO2. On the other hand, no apparent trends for these parameters were observed in the Pacific site. The contrasting results observed were probably due to the different plankton community compositions between the two sites, with plankton biomass dominated by large-sized diatoms in the Bering Sea versus ultra-eukaryotes in the Pacific Ocean. We conclude that the quantity and quality of the production of particulate and dissolved organic matter may be altered under future elevated CO2 environments in some iron-deficient ecosystems, while the impacts may be negligible in some systems.

The organic sea-surface microlayer in the upwelling region off the coast of Peru and potential implications for air-sea exchange processes

The sea-surface microlayer (SML) is at the upper- most surface of the ocean, linking the hydrosphere with the atmosphere. The presence and enrichment of organic compounds in the SML have been suggested to influence air- sea gas exchange processes as well as the emission of primary organic aerosols. Here, we report on organic matter components collected from an approximately 50µm thick SML and from the underlying water (ULW), ca. 20 cm below the SML, in December 2012 during the SOPRAN METEOR 91 cruise to the highly productive, coastal upwelling regime off the coast of Peru. Samples were collected at 37 stations including coastal upwelling sites and off-shore stations with less organic matter and were analyzed for total and dissolved high molecular weight (> 1 kDa) combined carbohydrates (TCCHO, DCCHO), free amino acids (FAA), total and dissolved hydrolyzable amino acids (THAA, DHAA), transparent exopolymer particles (TEP), Coomassie stainable particles (CSPs), total and dissolved organic carbon (TOC, DOC), total and dissolved nitrogen (TN, TDN), as well as bacterial and phytoplankton abundance. Our results showed a close coupling between organic matter concentrations in the water column and in the SML for almost all components except for FAA and DHAA that showed highest enrichment in the SML on average. Accumulation of gel particles (i.e., TEP and CSP) in the SML differed spatially. While CSP abundance in the SML was not related to wind speed, TEP abundance decreased with wind speed, leading to a depletion of TEP in the SML at about 5 m s-1 . Our study provides insight to the physical and biological control of organic matter enrichment in the SML, and discusses the potential role of organic matter in the SML for air-sea exchange processes.

Effect of enhanced pCO2 levels on the production of dissolved organic carbon and transparent exopolymer particles in short-term bioassay experiments

It has been proposed that increasing levels of pCO2 in the surface ocean will lead to more partitioning of the organic carbon fixed by marine primary production into the dissolved rather than the particulate fraction. This process may result in enhanced accumulation of dissolved organic carbon (DOC) in the surface ocean and/or concurrent accumulation of transparent exopolymer particles (TEPs), with important implications for the functioning of the marine carbon cycle. We investigated this in shipboard bioassay experiments that considered the effect of four different pCO2 scenarios (ambient, 550, 750 and 1000 µatm) on unamended natural phytoplankton communities from a range of locations in the northwest European shelf seas. The environmental settings, in terms of nutrient availability, phytoplankton community structure and growth conditions, varied considerably between locations. We did not observe any strong or consistent effect of pCO2 on DOC production. There was a significant but highly variable effect of pCO2 on the production of TEPs. In three of the five experiments, variation of TEP production between pCO2 treatments was caused by the effect of pCO2 on phytoplankton growth rather than a direct effect on TEP production. In one of the five experiments, there was evidence of enhanced TEP production at high pCO2 (twice as much production over the 96 h incubation period in the 750 ?atm treatment compared with the ambient treatment) independent of indirect effects, as hypothesised by previous studies. Our results suggest that the environmental setting of experiments (community structure, nutrient availability and occurrence of phytoplankton growth) is a key factor determining the TEP response to pCO2 perturbations.