14 th most abundant element in Earth s crust Sulfate is second most abundant anion in rivers (after bicarbonate) and in ocean after chloride
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1 Sulfur 14 th most abundant element in Earth s crust Sulfate is second most abundant anion in rivers (after bicarbonate) and in ocean after chloride Development of an oxygenated atmosphere facilitated this Aerosols (cloud condensation nuclei) Perturbed cycle Anthropogenic emissions of sulfur into the air are double natural emissions Acid rain, AMD Chemistry Variety of oxidation states II to +VI metal sulfides XS2 (-2) Hydrogen sulfide gas H2S (-2) FeS2 (-1) Sulfite SO2 3- (+5) Sulfate SO 4 2- (+6) Abundant so not limiting SO 4 2- is taken up by organisms and reduced to organic S Essential component of protein 1
2 60 61 Note may be as high as 120 dry deposition poorly understood WH by W.H. Schlesinger Schlesinger, / modified by S and B LOOK at table Active reservoirs (x g) Atmosphere Seawater 1280 Sedimentary rocks Evaporites 2470 Shales 4970 Land plants Soil organic Matter From S and B who took from Holser et al (1989) and Dobrovolsky (1994) 2
3 Atmosphere-short residence time Sources Biological (microbial) sources Volatile forms SO42- reduction Sulfate reduction can also lead to production of pyrite FeS2. Volcanic emissions SO2 Oceans Fossil fuel burning Dust and sea salt Microbial processes are important Wetland settings Chapter 7 Figure 7.10 and 7.18 Ocean setting Chapter pg 390 S&B Figure
4 Wetlands: brief introduction Wetland types 4
5 Hydric soils Mineral <20-35% organic Organic-primarily the remains of plants Histosols-muck and peat United States 53% lost in conterminous US from Agriculture Urban development 5
6 Control of nutrient cycles Redox Microbes Redox potential Measure of electron availability in a solution (negative more Used to quantify reduction Measured as Eh and is a quantitative measure of the soils ability to oxidize or reduce chemicals 6
7 From Mitsch and Gosselink, Wetlands (2000) 7
8 8
9 From Mitsch and Gosselink, From Mitsch and Gosselink, 9
10 From Mitsch and Gosselin k, Wetland s (2000) Oceans S species S and B Figure 9.29 Sources and sinks pg 390 Free ion SO 4 2- Second most abundant anion in the ocean Biological processes result in production of a variety of reduced forms 10
11 Microbes important in controlling forms In atmosphere most are reactive and have a short RT so deposited locally H2S Hydrogen sulfide-anaerobic setting-atmosphere CS2-Carbon disulfide precusor to OCS OCS-Carbonyl sulfide Table 13.3 (most abundant in atmosphere 5 yr RT) anoxic soils and industry and ocean (Source) plants and soils (Sink) Important source of stratosphere sulfate Organosulfides Methyl mercaptan CH3SH Dimethyl sulfide CH3SCH3 Dimethyl disulfide CH3SSCH3 Microbial processing Marine system sink- DMS to atmosphere Terrestrial and aquatic-h2s to atmosphere 11
12 OH radical important forms SO2 then SO42- that is deposited in precipitation DMSP (dimethylsulfoniopropionate) Produced within cells = Prymnesiophytes, Dinoflagellates Andreae 1990 Stress enhances release Species specific productionalso linked to nitrogen availability 12
13 Andreae paper Only certain organisms important Stress related release? Importance in cloud condensation nuclei Variation over glacial interglacial times S and B point to this also COS Carbonyl sulfide Most abundant sulfur species in the remote troposphere Not reactive long atmospheric residence time ~5 years In stratosphere important for maintaining sulfate aerosol Derived from abiotic photolysis of organic S compounds in seawater Oxidation of carbon disulfide-cs 2 emitted from anoxic soils and industry Table 13.3 Ocean is a sink Soils and vegetation are a sink 13
14 New work COS uptake through plant stomata may be a useful indicator of gross primary productivity COS due to long residence time-mixed to stratosphere Where, reactions with OH produce SO4 SO4 combines to produced aerosols Not increasing in atmosphere Coastal Marshes H2S, OCS, DMS, DMDS variable flux 14
15 Troposphere Residence time days SO4(2-) 1-2 days DMS Regional impacts Upper troposphere Aerosol S04 increasing over time Suggested due to aircraft. Dry deposition is poorly understood 15
16 16
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