How nitrate leaching from agricultural lands provokes phosphate eutrophication in groundwater fed wetlands: the sulphur bridge

Increased phosphorus availability may provoke serious eutrophication problems in wetlands. Strong evidence indicates that sulphate induced mobilization of phosphate (internal eutrophication) has been responsible for a strong decline of the biodiversity in wetlands during the last decades. It is currently underestimated, however, that the wide spread leaching of nitrate from agricultural lands can indirectly provoke strong internal phosphate eutrophication in wetlands, via its interference with sulphur and iron biogeochemistry in the subsoil. Nitrate can mobilize sulphate from geological pyrite deposits by the oxidation of FeS_x in the aquifer, leading to a decrease of nitrate and an increase of groundwater sulphate concentrations. Furthermore nitrate immobilizes iron in the subsoil by oxidizing reduced (dissolved) iron. Increased sulphate concentrations may provoke strong phosphate eutrophication in wetlands fed directly or indirectly (via surface water) with groundwater as sulphate strongly interferes with iron phosphorus chemistry and stimulates anaerobic decomposition of organic matter. Management of wetlands should therefore be approached at a broader scale which includes the landscape-scale management of groundwater systems. Leaching of nitrate to the groundwater, for instance, should not only receive attention for its potential effects on drinking water quality but above all because of the resulting large scale mobilization of sulphate from geological pyrite deposits and the immobilization of ferrous iron.     

Pyrite oxidation in acid sulphate soils: The role of miroorganisms

Summary A study has been made of microbial processes in the oxidation of pyrite in aicd sulphate soil material. Such soils are formed during aeration of marine muds rich in pyrite (FeS₂). Bacteria of the type ofThiobacillus ferrooxidans are mainly responsible for the oxidation of pyrite, causing a pronounced acidification of the soil. However, becauseThiobacillus ferrooxidans functions optimally at pH values bellow 4.0, its activity cannot explain the initial pH drop from approximately neutral to about 4. This was shown to be a non-biological process, in which bacteria play an insignificant part. AlthoughThiobacillus thioparus andThiobacillus thiooxidans were isolated from the acidifying soil, they did not stimulate oxidation of FeS₂, but utilized reduced sulphur compounds, which are formed during the non-biological oxidation of FeS₂.Ethylene-oxide-sterilized and dry-sterilized soil inoculated with pure cultures of mixtures of various thiobacilli or with freshly sampled acid sulphate soil soil did not acidify faster than sterile blanks.Thiobacillus thiooxians. Thiobacillus thioparus. Thiobacillus intermedius andThiobacillus perometabolis increased from about 10⁴ to 10⁵ cells/ml in media with FeS₂ as energy source. However, FeS₂ oxidation in the inoculated media was not faster than in sterile blanks.Attempts to isolate microorganisms other thanThiobacillus ferrooxidans, like metallogenium orLeptospirillum ferrooxidans, which might also be involved in the oxidation of FeS₂ were not successful.Addition of CaCO₃ to the soil prevented acidification but did not stop non-biological oxidation of FeS₂.     

生源要素有效性及生物因子对湿地土壤碳矿化的影响

湿地土壤是全球碳存储的重要场所,湿地生态系统的碳循环过程对全球变化有重要指示作用。土壤碳矿化是湿地生态系统碳循环的重要环节,对于认知湿地生态系统生物地球化学循环过程具有重要的意义。综述了生源要素及生物因素对湿地土壤碳矿化的内在作用机制。土壤活性有机碳库通过调节土壤能源物质和微生物活性影响土壤碳库的有效性,是表征土壤碳矿化的敏感指标。湿地其它养分如N、P、S等元素的有效性也是影响土壤碳矿化的关键要素。电子受体(NO₃^-、SO₄^2-、Fe³⁺、Mn⁴⁺等)对湿地土壤碳矿化和有机碳转变的影响主要通过电子受体的还原过程完成,在厌氧分解过程中,湿地土壤利用难溶性电子受体可能是土壤C矿化的更重要途径。动物、植物、微生物群落和区系等则是土壤碳矿化的主要驱动因子。土壤动物区系在有机态养分矿化为无机态养分的过程有着独特的功能,能显著增加土壤碳矿化。土壤微生物的活性,决定着土壤中有机碎屑的降解速率,是土壤有机碳分解周转的主要诱导因素。湿地植物则通过影响根系、微生物呼吸底物的供应以及对小气候和土壤因子的调节而影响土壤有机质的分解。湿地生源要素和生物因子还极易与土壤理化性质如温度、水分、pH值和质地等环境因素形成交互和制约,共同影响土壤碳矿化。最后,提出了进一步研究生源要素和生物因素与湿地土壤碳矿化关系需要解决的一些重要问题。     

Connecting carbon and nitrogen storage in rural wetland soil to groundwater abstraction for urban water supply

We investigated whether groundwater abstraction for urban water supply diminishes the storage of carbon (C), nitrogen (N), and organic matter in the soil of rural wetlands. Wetland soil organic matter (SOM) benefits air and water quality by sequestering large masses of C and N. Yet, the accumulation of wetland SOM depends on soil inundation, so we hypothesized that groundwater abstraction would diminish stocks of SOM, C, and N in wetland soils. Predictions of this hypothesis were tested in two types of subtropical, depressional‐basin wetland: forested swamps and herbaceous‐vegetation marshes. In west‐central Florida, >650 ML groundwater day^?1 are abstracted for use primarily in the Tampa Bay metropolis. At higher abstraction volumes, water tables were lower and wetlands had shorter hydroperiods (less time inundated). In turn, wetlands with shorter hydroperiods had 50–60% less SOM, C, and N per kg soil. In swamps, SOM loss caused soil bulk density to double, so areal soil C and N storage per m² through 30.5 cm depth was diminished by 25–30% in short‐hydroperiod swamps. In herbaceous‐vegetation marshes, short hydroperiods caused a sharper decline in N than in C. Soil organic matter, C, and N pools were not correlated with soil texture or with wetland draining‐reflooding frequency. Many years of shortened hydroperiod were probably required to diminish soil organic matter, C, and N pools by the magnitudes we observed. This diminution might have occurred decades ago, but could be maintained contemporarily by the failure each year of chronically drained soils to retain new organic matter inputs. In sum, our study attributes the contraction of hydroperiod and loss of soil organic matter, C, and N from rural wetlands to groundwater abstraction performed largely for urban water supply, revealing teleconnections between rural ecosystem change and urban resource demand.     

Soil-plant interactions in a neotropical mangrove forest: iron, phosphorus and sulfur dynamics

We examined soil porewater concentrations of sulfate, alkalinity, phosphorus, nitrogen, and dissolved organic carbon and solid phase concentrations of pyrite in relation to mangrove species distributions along a 3.1-km-long transect that traversed a 47.1-km² mangrove forest in the Dominican Republic. Iron, phosphorus, and sulfur dynamics are closely coupled to the activity of sulfate-reducing bacteria, the primary decomposers in anoxic soils of mangrove ecosystems. Patterns in the chemistry data suggested that sulfate reduction rates and storage of reduced sulfur were greater in the inland basin forest dominated by Laguncularia racemosa than the Rhizophora mangle dominated forest of the lower tidal region. The distribution of Laguncularia was significantly correlated with concentrations of total phosphorus (r= 0.99) and dissolved organic carbon (r= 0.86), alkalinity (r= 0.60), and the extent of sulfate depletion (r= 0.77) in the soil porewater and soil pyrite concentrations (r= 0.72) across the tidal gradient. Leaf tissue chemistry of Laguncularia was characterized by lower C:N and C:P ratios that could fuel the higher rates of decomposition in the Laguncularia-dominated forest. We suggest that a plant-soil-microbial feedback contributes to the spatial patterning of vegetation and soil variables across the intertidal zone of many mangrove forest communities. Received: 28 May 1997 / Accepted: 23 January 1998     

Enhanced Calcite Dissolution in the Presence of the Aerobic Methanotroph Methylosinus trichosporium

Microbial aerobic methane oxidation (MOx) is intrinsically coupled to the production of carbon dioxide, favoring carbonate dissolution. Recently, microbial organic polymers were shown to be able to induce carbonate dissolution. To discriminate between different mechanisms causing calcite dissolution, experiments were conducted in the presence of solid calcite with (1) actively growing cells (2) starving cells, and (3) dead cells of the methanotrophic bacterium Methylosinus trichosporium under brackish conditions (salinity 10) near calcite saturation (saturation state (Ω) 1.76 to 2.22). Total alkalinity and the amount of dissolved calcium markedly increased in all experiments containing M. trichosporium cells. After initial system equilibration, similar calcite dissolution rates, ranging between 20.16 (dead cells) and 25.68 μmol L^?1 d^?1 (actively growing cells), were observed. Although concentrations of transparent exopolymer particles declined with time in the presence of actively growing and starving cells, they increased in experiments with dead cells. Scanning electron microscopy images of calcite crystals revealed visible surface corrosion after exposure to live and dead M. trichosporium cells. The results of this study indicate a strong potential for microbial MOx to affect calcite stability negatively, facilitating calcite dissolution. In addition to CO₂ production by methanotrophically active cells, we suggest that the release of acidic or Ca²⁺-chelating organic carbon compounds from dead cells could also enhance calcite dissolution.     

Cyanobacterial calcification and its rock-building potential during 3.5 billion years of Earth history

Microbially mediated calcification can be traced back for at least 2.6 billion years. Although morphological comparison of fossil and recent microbial carbonates suggests that mineralization processes associated with cyanobacteria and their interactions with heterotrophic bacteria have remained similar from the Archaean until today, the metabolic and chemical details remain poorly constrained. Microbial consortia often exhibit an ability to change solution chemistry and control pH at the microscale, passively or actively. This leads to oversaturation of Ca²⁺ and ions and to the removal of kinetic inhibitors to carbonate precipitation, like sulphate or phosphate. The kinetic barriers of low carbonate ion activity, ion hydration and ion complexing, especially in saline waters, inhibit spontaneous carbonate mineral precipitation from saturated solutions but oxygenic photosynthesis and sulphate reduction by sulphate‐reducing bacteria can overcome these natural barriers. Sulphate in seawater tends to form pairs with Ca²⁺ and Mg²⁺ ions. The removal of sulphate reduces complexing, raises carbonate alkalinity, and along with pyrite formation, enhances carbonate precipitation. Cyanobacteria can store Ca²⁺ and Mg²⁺ ions in organic envelopes and precipitate carbonates within their sheaths and extracellular polymeric substances, thus, triggering sedimentary carbonate production. We propose that this interplay of cyanobacteria and heterotrophic bacteria has been the major contributor to the carbonate factory for the last 3 billion years of Earth history.     

A new occurrence of ambient inclusion trails from the ~1900‐million‐year‐old Gunflint Formation,Ontario: nanocharacterization and testing of potential formation mechanisms

Ambient inclusion trails (AITs) are tubular microstructures thought to form when a microscopic mineral crystal is propelled through a fine‐grained rock matrix. Here, we report a new occurrence of AITs from a fossilized microbial mat within the 1878‐Ma Gunflint Formation, at Current River, Ontario. The AITs are 1–15 μm in diameter, have pyrite as the propelled crystal, are infilled with chlorite and have been propelled through a microquartz (chert) or chlorite matrix. AITs most commonly originate at the boundary between pyrite‐ and chlorite‐rich laminae and chert‐filled fenestrae, with pyrite crystals propelled into the fenestrae. A subset of AITs originate within the fenestrae, rooted either within the chert or within patches of chlorite. Sulphur isotope data (³⁴S/³²S) obtained in situ from AIT pyrite have a δ³⁴S of ?8.5 to +8.0 ‰, indicating a maximum of ~30 ‰ fractionation from Palaeoproterozoic seawater sulphate (δ³⁴S ≈ +20 ‰). Organic carbon is common both at the outer margins of the fenestrae and in patches of chlorite where most AITs originate, and can be found in smaller quantities further along some AITs towards the terminal pyrite grain. We infer that pyrite crystals now found within the AITs formed via the action of heterotrophic sulphate‐reducing bacteria during early diagenesis within the microbial mat, as pore waters were becoming depleted in seawater sulphate. Gases derived from this process such as CO₂ and H₂S were partially trapped within the microbial mat, helping produce birds‐eye fenestrae, while rapid microquartz precipitation closed porosity. We propose that propulsion of the pyrite crystals to form AITs was driven by two complementary mechanisms during burial and low‐grade metamorphism: firstly, thermal decomposition of residual organic material providing CO₂, and potentially CH₄, as propulsive gases, plus organic acids to locally dissolve the microquartz matrix; and secondly, reactions involving clay minerals that potentially led to enhanced quartz solubility, plus increases in fluid and/or gas pressure during chlorite formation, with chlorite then infilling the AITs. This latter mechanism is novel and represents a possible way to generate AITs in environments lacking organic material.     

Effects of long-term soil acidification due to nitrogen fertilizer inputs in Wisconsin

Agroecosystems are domesticated ecosystems intermediate between natural ecosystems and fabricated ecosystems, and occupy nearly one-third of the land areas of the earth. Chemical perturbations as a result of human activity are particularly likely in agroecosystems because of the intensity of that activity, which include nutrient inputs intended to supplement native nutrient pools and to support greater biomass production and removal. At a long-term fertility trial in South-Central Wisconsin, USA, significant increases in exchangeable acidity were accompanied by decreases in cation exchange capacity (CEC), base saturation, and exchangeable Ca²⁺ and Mg²⁺ with application of ammoniacal N fertilizer. Plant analysis shows that a considerable portion of the alkalinity generated by assimilation of N (and to a lesser extent by S) is sequestered in the above-ground plant parts as organic anions and is not returned to the soil if harvested. Elemental analysis of Ca-saturated soil clays indicates an loss of 16% of the CEC of the soil clay and minor increases in Fe and Al. The reversibility of these changes due to prolonged acidification is doubtful if the changes are due to soil weathering.     

Vegetation composition of Lolium perenne-dominated grasslands under organic and conventional farming

Agricultural intensification has caused a decline of semi-natural grasslands and loss of botanical diversity, making agricultural fields dominated by Lolium perenne the main grassland system in large areas of Europe. Increased insight into the factors determining their vegetation composition and plant species richness is needed to improve the effectiveness of agri-environment schemes and to substantiate the benefits of organic over conventional agriculture. Our aims were (1) to determine the difference in vegetation composition (including species richness) between Lolium perenne-dominated fields of conventional and organic farms in a case study region in The Netherlands, and (2) to identify the soil and management related drivers behind this difference.We collected vegetation, soil and management data in grasslands of dairy farms under conventional or organic management (45 fields in total), and used multivariate statistics to determine the effect of fertilisation rates, grazing and cutting regime, and soil properties on plant species composition. In a next step we determined to what extent these abiotic drivers differ between organic and conventional farms.On average the organic fields appeared to have a c. 30% higher plant species richness compared to the conventional ones. Vegetation composition was most strongly influenced by groundwater level and nitrogen and phosphorus fertilisation rates, and to a lesser extent by plant-available soil potassium, mowing date, total soil nitrogen, potassium fertilisation rate, age of each field, and livestock (cow or sheep). In general, a low fertilisation rate, high groundwater level, late mowing, low level of plant-available potassium, high level of total soil nitrogen, old fields and the presence of sheep promote a high species richness. However, of these variables only nitrogen fertilisation rate and groundwater level differ significantly between the organic and conventional farms and are therefore likely to be the abiotic drivers of the difference in species richness and vegetation composition between the farm types. Of these two, the difference in nitrogen fertilisation rate is a direct result of a difference in management philosophy, but the difference in groundwater level is not. We hypothesize that the latter difference is caused by economic drivers, whereby a less productive soil is an incentive for a changeover to organic farming. If this is the case indeed, the application of agri-environment schemes would be most effective in less productive (and naturally more species-rich) sites.     

Response of wetland soil carbon to groundwater conservation: Probabilistic outcomes from error propagation

Water loss compromises functions performed by wetland ecosystems. Efforts to rehabilitate wetland function typically begin with attempts to reestablish hydrology. These activities are often not monitored, so tools to extract information from them could partly offset the lost opportunity to learn from whole-ecosystem hydrological manipulation. In 2002, groundwater abstraction was lessened by 35% throughout 1700 km² of west-central Florida (USA). I assembled a pathway of correlations to project how this hydrological manipulation affected water levels and soil carbon (C) storage in overlying wetlands. Parameter values and residual error in these statistical models were resampled from known variances, thereby propagating uncertainty through the pathway of relationships, and expressing the response of soil C probabilistically. Projected soil C probability distributions were most distinguishable between full and moderate (30% less) abstraction. With more severe abstraction cutbacks, gains in projected soil C became more marginal and uncertain, suggesting that wetland soil C pools are not notably impacted by low-volume groundwater abstraction. Reducing uncertainty in projected soil C will require better understanding the dynamic response of soil C to increases in the amount of time that wetland soil is inundated. The step-by-step error propagation routine presented here is a platform for assimilating information from diverse sources in order to project probabilistic responses of ecosystem function to wetland restoration attempts, and it helps identify where further certainty is most wanted in a pathway of cause–effect relationships.     

Variation in soil phosphorus, sulfur, and iron pools among south Florida wetlands

To determine relationships between soil nutrient status and known gradients in primary production, we collected and analyzed soils from 17 LTER sampling sites along two transects through south Florida wetland ecosystems. Through upstream freshwater marsh, a middle reach including the oligohaline marsh/mangrove ecotone, and downstream estuarine habitats, we observed systematic variation in soil bulk density, organic content, and pools of phosphorus (P), inorganic sulfur, and extractable iron. Consistent with observed differences in wetland productivity known to be limited by P availability, total P averaged ~200 μg g dw⁻¹ in soils from the eastern Taylor Slough/Panhandle and was on average three times higher in soils from the western Shark River Slough. Along both transects, the largest pool of phosphorus was the inorganic, carbonate-bound fraction, comprising 35–44% of total P. Greater than 90% of the total inorganic sulfur pool in these south Florida wetland soils was extracted as pyrite. Freshwater marsh sites typically were lower in pyrite sulfur (0.2–0.8 mg g dw⁻¹) relative to marsh/mangrove ecotone and downstream estuary sites (0.5–2.9 mg g dw⁻¹). Extractable iron in freshwater marsh soils was significantly higher from the Taylor Slough/Panhandle transect (3.2 mg g dw⁻¹) relative to the western Shark River Slough transect (1.1 mg g dw⁻¹), suggesting spatial variation in sources and/or depositional environments for iron. Further, these soil characteristics represent the collective, integrated signal of ecosystem structure, so any long-term changes in factors like water flow or water quality may be reflected in changes in bulk soil properties. Since the objective of current Everglades restoration initiatives is the enhancement and re-distribution of freshwater flows through the south Florida landscape, the antecedent soil conditions reported here provide a baseline against which future, post-restoration measurements can be compared.     

湖南乌云界自然保护区典型生态系统的土壤持水性能

土壤持水性能是决定生态系统水源涵养能力的关键,是自然保护区生态服务功能的重要方面。以湖南省乌云界自然保护区为研究区域,选取森林、灌丛、竹林和草地4个典型生态系统,采用野外调查采样和室内分析的方法研究了土壤的物理性质和持水性能。结果表明,乌云界4种典型植被下表层0—20cm土壤有机质含量普遍较高(>76 g/kg)、容重较低(<0.85 g/cm3)、团聚体稳定性较强(>5mm水稳性团聚体达22.7%—52.3%),表明保护区土壤的结构发育总体上较好。森林和竹林土壤具有较多的大孔隙和较高的饱和导水率,有利于天然降水向地下水的转化,而灌丛和草地土壤毛管孔隙度则相对较高,其土壤中能够保持更多的有效水分。乌云界自然保护区4个典型生态系统0—40cm土层土壤重力水容量为:森林(83.5 mm)>竹林(79.2mm)>灌丛(66.9 mm)>草地(43.8 mm),有效水容量为:草地(128.7 mm)>灌丛(111.6 mm)>森林(95.9 mm)>竹林(83.9mm)。在明晰土壤总蓄水容量(>0 MPa)、重力水容量(0—0.01 MPa)、有效水容量(0.01—1.5 MPa)、无效水容量(>1.5 MPa)等概念的基础上,建议用重力水容量和土壤有效水容量两个指标来评价生态系统土壤的水源涵养功能,其中土壤重力水容量可以反映生态系统补充地下水和调控河川径流量的能力,而土壤有效水容量可以反映生态系统本身保蓄水分的潜力,这些指标均可以通过土壤水分特征曲线进行求算。乌云界自然保护区森林和竹林土壤对于补充地下水和调控河川径流量的能力较强,而灌丛和草地土壤保蓄水分的能力较强。     

Forest sources and pathways of organic matter transport to a blackwater stream: a hydrologic approach

Quantitative information regarding landscape sources and pathways of organic matter transport to streams is important for assessing impacts of terrestrial processes on aquatic ecosystems. We quantified organic C, a measure of organic matter, flowing from a blackwater stream draining a 12.6 km² watershed on the upper Atlantic Coastal Plain in South Carolina, and utilized a hydrologic approach to partition this outflow between its various pathways from upland and wetland forest sources. Results of this study indicate that 28.9 tonnes C yr^–1 were exported in stream flow, which was estimated to be 0.5% of the annual C input from forest detritus to the watershed. Upland forest, which covers 94% of the watershed area, contributed only 2.0 tonnes C yr^–1 to stream flow, which amounted to 0.04% of detritus annually produced by the upland forest. Organic matter was transported from uplands to the stream almost entirely through groundwater. Apparently, upland soils are too sandy to support overland flow, and the sloping topography insufficiently extensive or steep enough to drive important quantities of interflow. Riparian wetland forest, which covers only 6% of the watershed area, contributed 26.9 tonnes C yr^–1 to stream flow, amounting to about 10.2% of detritus annually produced by the wetland forest. Dissolved organic C leached from wetland soil accounted for 63% of all organic C entering the stream, and was transported chiefly in baseflow. These results indicate that upland detritus sources are effectively decoupled from the stream despite the sandy soils and quantitatively confirm that even small riparian wetland areas can have a dominant effect on the overall organic matter budget of a blackwater stream. In view of the recognized importance of dissolved organic matter in facilitating transport of other substances (e.g., cation nutrients, metals, and insoluble organic compounds), our results suggest that the potential for movement of these substances through wetland soils to streams in this region is high.     

Temporal and spatial development of soil solution chemistry and element budgets in different mine soils of the Lusatian lignite mining area

Lignite and pyrite contents in the dump materials of the Lusatian opencast mining district in East Germany result in high acidification and salinization potentials. These extreme conditions require considerable amounts of alkaline materials like ash or lime to enable recultivation and revegetation. Investigations at chronosequence sites on different mining substrates show characteristic developments of the soil solution chemistry. Processes like weathering of primary and formation of secondary mineral phases, acid production and buffering, and their impacts on both the solid and the liquid soil phase result in high temporal and spatial dynamics especially in the initial phase of soil and ecosystem development. To study these processes we continuously collected soil solutions from different soil depths at seven sites with two representative soil substrates. All sites were afforested with pine and cover stand ages from 1 to 60 yr. The results show that actual pyrite oxidation occurs at the youngest sites on lignite and pyrite containing substrates leading to extremely low pH values and high Feⁿ⁺ and SO₄ ²- concentrations. The considerable acid production causes weathering of aluminium silicates resulting in high Alⁿ⁺ concentrations. Ca²⁺ concentrations are unexpectedly high even at low pH showing no correlation to amelioration amounts or depths. Therefore it seems most probable that these mining substrates contain geogenic Ca sources. The transport of dissolved weathering products is limited due to low leaching rates enabling formation of secondary phases which control the actual composition of the soil solution. Depth gradients of the soil solution composition at the chronosequence sites point to a gradual transport and leaching of these secondary phases from the soil profiles. Soil solution composition and dynamics at lignite and pyrite free sites show completely different patterns and have a higher potential for successful sustainable recultivation. This revised version was published online in June 2006 with corrections to the Cover Date. This revised version was published online in June 2006 with corrections to the Cover Date. This revised version was published online in June 2006 with corrections to the Cover Date.     

Miocene methane‐derived carbonates from southwestern Washington,USA and a model for silicification at seeps

Kuechler, R.R., Birgel, D, Kiel, S, Freiwald, A, Goedert, J.L., Thiel, V & Peckmann, J. 2011: Miocene methane‐derived carbonates from southwestern Washington, USA and a model for silicification at seeps. Lethaia, Vol. 45, pp. 259–273. Exotic limestone masses with silicified fossils, enclosed within deep‐water marine siliciclastic sediments of the Early to Middle Miocene Astoria Formation, are exposed along the north shore of the Columbia River in southwestern Washington, USA. Samples from four localities were studied to clarify the origin and diagenesis of these limestone deposits. The bioturbated and reworked limestones contain a faunal assemblage resembling that of modern and Cenozoic deep‐water methane‐seeps. Five phases make up the paragenetic sequence: (1) micrite and microspar; (2) fibrous, banded and botryoidal aragonite cement, partially replaced by silica or recrystallized to calcite; (3) yellow calcite; (4) quartz replacing carbonate phases and quartz cement; and (5) equant calcite spar and pseudospar. Layers of pyrite frequently separate different carbonate phases and generations, indicating periods of corrosion. Negative δ¹³C_carbonate values as low as ?37.6‰ V‐PDB reveal an uptake of methane‐derived carbon. In other cases, δ¹³C_carbonate values as high as 7.1‰ point to a residual, ¹³C‐enriched carbon pool affected by methanogenesis. Lipid biomarkers include ¹³C‐depleted, archaeal 2,6,10,15,19‐pentamethylicosane (PMI; δ¹³C: ?128‰), crocetane and phytane, as well as various iso‐ and anteiso‐carbon chains, most likely derived from sulphate‐reducing bacteria. The biomarker inventory proves that the majority of the carbonates formed as a consequence of sulphate‐dependent anaerobic oxidation of methane. Silicification of fossils and early diagenetic carbonate cements as well as the precipitation of quartz cement – also observed in other methane‐seep limestones enclosed in sediments with abundant diatoms or radiolarians – is a consequence of a preceding increase of alkalinity due to anaerobic oxidation of methane, inducing the dissolution of silica skeletons. Once anaerobic oxidation of methane has ceased, the pH drops again and silica phases can precipitate. □Biomarkers, carbonates, isotopes, methane, Miocene, silicification, Washington.     

The relation between vegetation and soil chemistry gradients in a ground water discharge fen

Abstract. The soil chemistry of a headwater valley fen is influenced by local ground water discharge that supplies base cations and alkalinity to the fen. An irrigation canal just upward of the fen is the source of this alkalinity. The ecological consequences of this artificial system are studied both on the soil and vegetation level. Rich-fen species of the alliance Caricion davallianae are connected to soil water alkalinity and soil base status. They depend directly on the alkaline ground water discharge. In addition, the local input of this water causes a gradient-rich pattern from poor to rich fen, and it is therefore concluded that it is responsible for the presence of intermediate fen vegetation too. High nutrient levels in the irrigation water have not influenced the fen until now. This case study illustrates the possibility for rich fen restoration after acidification. Irrigation with alkaline water is efficient if excess nutrients can be removed.     

Groundwater input affecting plant distribution by controlling ammonium and iron availability

Question: How does groundwater input affect plant distribution in Alnus glutinosa (black alder) carrs? Location: Alder carrs along the river Meuse, SE Netherlands. Methods: Three types of site, characterized by groundwater flow, were sampled in 17 A. glutinosa carrs. Vegetation and abiotic data (soil and water chemistry) were collected and analysed using a Canonical Correspondence Analysis. Based on the results, a laboratory experiment tested the effect of groundwater input (Ca²⁺) on pore water chemistry (NH₄⁺ availability). Results: Environmental factors indicating groundwater input (Ca²⁺ and Fe²⁺), correlating with the NH⁺₄ concentration in the pore water, best explained the variation in plant distribution. NH₄⁺ availability was determined by Ca²⁺ input via the groundwater and subsequent competition for exchange sites in the sediment. As a result, nutrient‐poor seepage locations fully fed by groundwater were dominated by small iron resistant plants such as Caltha palustris and Equisetum fluviatile. More nutrient‐rich locations, fed by a combination of groundwater and surface water, allowed the growth of taller iron resistant plant species such as Carex paniculata. Nutrient‐rich locations with stagnating surface water were hardly fed by groundwater, allowing the occurrence of fast growing and less iron tolerant wetland grasses such as Glyceria fluitans and G. maxima. Conclusion: Groundwater input affects plant composition in A. glutinosa carrs along the river Meuse by determining nutrient availability (ammonium) and concentrations of toxic iron.     

Biogeochemical interactions between iron and sulphate in freshwater wetlands and their implications for interspecific competition between aquatic macrophytes

1. Wetlands are threatened by desiccation, eutrophication and changing water quality, generally leading to greatly altered biogeochemical processes. Sulphate pollution can lead to severe eutrophication and sulphide toxicity, but may also interact with the availability of iron and other metals. 2. In the present study, we examined the biogeochemical interactions between sulphate and iron availability, and their effects on aquatic macrophytes, in a field experiment with enclosures. The natural iron supply by groundwater was mimicked by adding iron to the sediment, and the effect of increased sulphate concentrations in the surface water was also studied. The enclosure experiment was performed in a mesotrophic, anaerobic ditch in a peat meadow reserve in the Netherlands. In all enclosures, three Stratiotes aloides plants were introduced to serve as indicator species. 3. Addition of sulphate led to the mobilisation of phosphate, whereas addition of iron or both iron and sulphate did not affect P mobilisation. Growth of S. aloides was decreased by both iron addition and sulphate addition (sulphide toxicity). Addition of iron under sulphidic conditions, however, led to mutual detoxification of both toxicants (iron and sulphide) and did not decrease S. aloides growth. The uptake of metals was highest in the treatment involving sulphate addition, probably as a result of increased mineralisation of the peat soil. 4. Growth of Elodea nuttallii, which grew naturally in the enclosures, was stimulated by iron or iron plus sulphate addition. It did not, however, grow in the enclosures with sulphate addition, as a result of sulphide toxicity or sulphide‐induced iron deficiency. Under iron‐rich conditions, E. nuttallii appeared to be a better competitor than S. aloides and depressed the growth of the latter species. 5. We propose that the growth of S. aloides is directly regulated by interactions between sulphide and iron and indirectly by the effects of both compounds on the competitive strength of E. nuttallii. In general, we conclude that biogeochemical interactions between sulphate and iron can have a strong influence on plant species composition in freshwater wetlands, because of direct effects or changes in the competitive strength of plant species related to differential sensitivity to either iron or sulphide.     

滨海湿地生态系统微生物驱动的氮循环研究进展

滨海湿地生态系统介于陆地生态系统和海洋生态系统之间,其类型多种多样,环境差异极大,微生物种类丰富。近年来,随着人为氮源的大量输入,造成滨海湿地生态系统富营养化污染问题日趋严重。本文主要总结了滨海湿地生态系统微生物驱动的固氮、硝化、反硝化、厌氧氨氧化、NO_3~-还原成铵等主要氮循环过程,并综述了通过功能基因(如nifH、amoA、hzo、nirS、nirK、nrfA)检测微生物群落多样性及其环境影响因素的相关研究,旨在更好理解微生物驱动氮循环过程以去除氮,以期为减轻富营养化和危害性藻类爆发提供科学依据。