Significance of vertical flux as a sink for surface water DMSP and as a source for the sediment surface in coastal zones of northern Europe

In April 1997 and 1998 the significance of sedimentation as a sink for epipelagic dimethylsulphoniopropionate (DMSP) production and as a source for marine sediments was reassessed using a newly designed sediment trap. The behaviour of the traps in immersion was monitored continuously and the collection efficiency was evaluated with ²³⁴Th measurements. Net DMS(P) fluxes were corrected for some physical and biological losses during the whole sedimentation process providing reliable estimates of gross DMSP fluxes. It is shown that daily losses by sedimentation account for between 0.1% and 16% of seawater particulate DMSP (DMSPp) standing stocks, and between 3% and 75% of daily DMSPp production. In the Malangen fjord we observed temporal increases of DMSP production and standing stocks which resulted also in increases of DMSP vertical fluxes and DMS(P) concentrations at the sediment surface. This result illustrates how tight the coupling can be between pelagos and benthos, and confirms that DMS(P) concentration in the sediment was a reliable diagnostic indicator of vertical export from overlying waters in Malangen fjord. In Ullsfjord, however, DMS(P) concentrations in the sediment were poorly indicators of Phaeocystis pouchetii export during the early stage of growth of a bloom. The high load of DMS(P) in Balsfjord's sediments could neither be attributed to local vertical sedimentation nor to short-term lateral advection of fresh DMSP-containing phytoplanktonic material, and provides indication that this tracer sometimes also can be misleading. The highest loads of DMS(P) in sediments and the fastest rates of sedimentation occurred in the Southern Bight of the North Sea.     

Physiological aspects of the production and conversion of DMSP in marine algae and higher plants

Dimethylsulphoniopropionate (DMSP) is a compound produced in several classes of algae and higher plants that live in the marine environment. Considering its generally high intracellular concentrations, DMSP has a function in the osmotic protection of algal cells. Due to the relatively slow adaptation of its intracellular concentrations upon salinity shifts, DMSP should, however, not be considered as an osmoticum in the strict sense of being responsible for osmotic balance, but rather as a constitutive compatible solute. Besides salinity, other factors also appear to affect cellular DMSP quotas, but the exact regulatory mechanisms are still unclear. In this review, a brief discussion is given of the three pathways of DMSP biosynthesis that are currently distinguished. This is followed by an overview of the factors that affect DMSP biosynthesis (light, salinity, temperature and nitrogen limitation) in relation to its physiological functions. A new hypothesis is presented in which DMSP production is described as an overflow mechanism for excess reduced compounds and for energy excess. Finally, the possible functionality of the enzymatic cleavage of DMSP is discussed in the context of an overflow mechanism.     

Determinations of dimethylsulphoniopropionate (DMSP) lyase activity using headspace analysis of dimethylsulphide (DMS)

The osmolyte dimethylsulphoniopropionate (DMSP) can be enzymatically cleaved to dimethylsulphide (DMS), acrylate and a proton. The enzyme involved in this reaction is dimethylpropiothetin dethiomethylase (DMSP lyase; enzyme classification number 4.4.1.3.). Although the importance of this reaction for the global sulphur cycle, the influence of DMS on atmospheric acidity and the possible effect on climate regulation have been widely recognised, our knowledge of DMSP lyases is limited to just a few studies. Activity measurements of DMSP lyases offer an important step towards a better understanding of the conditions under which DMS is produced. In the available published data somewhat similar methods have been used before, but a critical examination of the method limitations has not been reported. To encourage further research on this enzyme, we suggest and detail two protocols for measurements of DMSP lyase activity: An in vitro assay for crude cell extracts or purified enzyme and an in vivo method for whole cells, which we recently started to use. After addition of DMSP, samples incubated in a gas tight vial may produce DMS from enzymatic cleavage under suitable conditions, and a DMS production rate can be estimated from time-series measurements of DMS in the headspace of the vial. Headspace analysis of DMS is a useful and rapid technique to estimate and compare DMSP lyase activities from different sources. The relative rates of DMS production in the liquid and of the gas transfer between liquid and headspace, determine the rate of DMS production measured via headspace analysis. If DMS production in the liquid is higher than the rate of transfer, headspace measurements will not reflect the actual amount of DMS produced in the liquid. In this case, extracts have to be diluted to a level that ensures linearity between dilution factor and reduction of enzyme activity. Additionally, incubation volumes and vials should be selected to provide a high surface-to-volume ratio to ensure maximum flux of DMS from the aqueous phase into the headspace. The methods can be adapted to further investigate species- and strain-specific activities, biogeographical distribution, cellular location and biochemical properties of various DMSP lyases.     

海洋中二甲基亚砜的来源、分布及迁移转化

二甲基亚砜(DMSO)是海水中的主要溶解态甲基硫化物,DMSO在二甲基硫(DMS)的生物地球化学循环中起着重要的作用。它能通过DMS的光化学氧化和细菌氧化生成,可作为DMS的1个汇,也可以通过生物直接合成或其它途径产生。DMSO同时又可以被酶、细菌、植物等还原为DMS,因此,DMSO又可充当DMS的1个源。DMSO除了能被还原为DMS外,还可能会被细菌氧化为SO42-,在氯过氧化物酶作用下被H2O2氧化为DMSO2等。海洋中DMSO的测定通常采用还原剂NaBH4将其还原为DMS后,再利用气相色谱进行测定。海水中DMSO的分布不均匀,高浓度区是那些温度较高,光照充足、浮游植物较多、生物活性较高的表层水或近岸水。     

Influence of Transport over a Mountain Ridge on the Chemical Composition of Marine Aerosols during the ACE-2 Hillcloud Experiment

Aerosol chemical composition and trace gas measurements were made at twolocations on the northeastern peninsula of Tenerife during the ACE-2HILLCLOUD experiment, between 28 June and 23 July 1997. Measurementswere made of coarse (#gt;2.5 m aerodynamic diameter) and fine (#lt; 2.5m) aerosol Cl^–, NO₃ ^–,SO₄ ^2–, non-sea saltSO₄ ^2– (NSSS),CH₃SO₃ ^– (MSA) andNH₄ ⁺, and gas phase dimethylsulphide (DMS), HCl,HNO₃, SO₂, CH₃COOH, HCOOH andNH₃. Size distributions were measured using a cascadeimpactor. Results show that in marine air masses NSSS and MSA wereformed via DMS oxidation, with additional NSSS present in air massescontaining a continental component. Using a Eulerian box model approachfor aerosols transported between upwind and downwind sites, a mean NSSSproduction rate of 4.36 × 10^–4 gm^–3 s^–1 was calculated for daytimeclear sky periods (highest insolation), with values for cloudy periodsduring daytime and nighttime of 3.55 × 10^–4 and2.40 × 10^–4 g m^–3s^–1, respectively. The corresponding rates for MSA were6.23 × 10^–6, 8.49 × 10^–6and 6.95 × 10^–6 g m^–3s^–1, respectively. Molar concentration ratios forMSA/NSSS were 8.7% (1.8–18.2%) and 1.9%(1.3–3.5%) in clean and polluted air masses, respectively.Reactions occurring within clouds appeared to have a greater influenceon rates of MSA production, than of NSSS, while conversely daytime gasphase reactions were more important for NSSS. For MSA, nighttimein-cloud oxidation rates exceeded rates of daytime gas phase productionvia OH oxidation of DMS. NSSS, MSA and ammonium had trimodal sizedistributions, with modes at 0.3, 4.0 and >10.0 m (NSSS andNH₄ ⁺), and 0.3, 1.5 and 4.0 m (MSA). Nosignificant production of other aerosol species was observed, with theexception of ammonium, which was formed at variable rates dependent onneutralisation of the aerosol with ammonia released from spatiallynon-uniform surface sources. Seasalt components were mainly present incoarse particles, although sub-micrometre chloride was also measured.Losses by deposition exceeded calculated expectations for all species,and were highest for the seasalt fraction and nitrate.