Dissolved organic carbon and volatile fatty acids in marine sediment pore waters

The results of a study of the contribution of microbial metabolic products to total dissolved organic carbon (DOC) levels in coastal sediments are presented. The data indicate that acidic volatile compounds make up a substantial fraction of pore water DOC's in both oxic and anoxic pore waters of coastal marine sediments. Formic, acetic and butyric acids are the principal volatile species identified at levels exceeding 10 μM. Acid concentrations are up to five times higher in anoxic pore waters than in oxic waters. Volatile organic acids show promise as indicators of diagenetic processes in marine sediments and of the ecological succession of microorganisms, in particular.     

Adsorption of natural dissolved organic matter at the oxide/water interface

Natural organic matter is readily adsorbed by alumina and kaolinite in the pH range of natural waters. Adsorption occurs by complex formation between surface hydroxyls and the acidic functional groups of the organic matter. Oxides with relatively acidic surface hydroxyls, e.g. silica, do not react strongly with the organic matter. Under conditions typical for natural waters, almost complete surface coverage by adsorbed organic matter may be expected for alumina, hydrous iron oxides and the edge sites of aluminosilicates. Potentiometric titration and electrophoresis indicate that most of the acidic functional groups of the adsorbed organic matter are neutralized by protons from solution. The organic coating is expected to have a great influence on subsequent adsorption of inorganic cations and anions.     

Mercury Dynamics in a San Francisco Estuary Tidal Wetland: Assessing Dynamics Using In Situ Measurements

We used high-resolution in situ measurements of turbidity and fluorescent dissolved organic matter (FDOM) to quantitatively estimate the tidally driven exchange of mercury (Hg) between the waters of the San Francisco estuary and Browns Island, a tidal wetland. Turbidity and FDOM??representative of particle-associated and filter-passing Hg, respectively??together predicted 94?% of the observed variability in measured total mercury concentration in unfiltered water samples (UTHg) collected during a single tidal cycle in spring, fall, and winter, 2005?C2006. Continuous in situ turbidity and FDOM data spanning at least a full spring-neap period were used to generate UTHg concentration time series using this relationship, and then combined with water discharge measurements to calculate Hg fluxes in each season. Wetlands are generally considered to be sinks for sediment and associated mercury. However, during the three periods of monitoring, Browns Island wetland did not appreciably accumulate Hg. Instead, gradual tidally driven export of UTHg from the wetland offset the large episodic on-island fluxes associated with high wind events. Exports were highest during large spring tides, when ebbing waters relatively enriched in FDOM, dissolved organic carbon (DOC), and filter-passing mercury drained from the marsh into the open waters of the estuary. On-island flux of UTHg, which was largely particle-associated, was highest during strong winds coincident with flood tides. Our results demonstrate that processes driving UTHg fluxes in tidal wetlands encompass both the dissolved and particulate phases and multiple timescales, necessitating longer term monitoring to adequately quantify fluxes.     

Assessment of the geochemical reactivity of Fe-DOM complexes in wetland sediment pore waters using a nitroaromatic probe compound

The reductive capacity of Fe(II) present in anoxic sediment pore waters affects biogeochemically significant processes that occur in these environments, such as metal speciation, mineral solubility, nutrient bioavailability, and the transformation of anthropogenic organic compounds. We studied the reduction of pentachloronitrobenzene (PCNB) in natural pore waters to elucidate the reductive capacity of Fe(II) complexes, and monitored the redox-active species responsible for the observed kinetics. Differential pulse polarography (DPP) scans of sediment pore waters from a coastal Lake Erie wetland (Old Woman Creek National Estuarine Research Reserve, Huron, OH) revealed an increase in both Fe(III)-organic and Fe(II) species to a depth of ∼30 cm below the sediment-water interface. Concentrations of dissolved organic matter (DOM) in pore waters increased while pH decreased with depth. We found that Fe(II) was necessary for rapid PCNB reduction (<24 h), and observed faster reduction with increased pH. PCNB reduction in preserved pore waters (acidified to pH 2.5 after pore water extraction and raised to the native pH (6.7-7.6) prior to reaction) was similar to that observed in a model system containing Fe(II) and fulvic acid isolated from this site. Conversely, PCNB reduction in unaltered pore water was significantly slower than that observed in preserved pore water, indicating that the Fe(II) speciation and its reductive capacity differed. DPP scans of pore waters used for kinetic studies confirmed that pH-adjustment affected Fe_T speciation in the pore waters, as the Fe(III)-DOM peak current was lowered or disappeared completely in the preserved pore water samples. These data show that pH-adjustment of pore waters presumably alters both their complexation chemistry and reactivity towards PCNB, and shows how small changes in Fe complexation can potentially affect redox chemistry in anoxic environments. Our results also show that reactive organic Fe(II) complexes are naturally present in wetland sediment pore waters, and that these species are potentially important mediators of Fe(II)/Fe(III) redox biogeochemistry in anoxic sedimentary environments.     

Hydrogeochemical investigation of Küçük Menderes River coastal wetland,Selçuk–Izmir,Turkey

Küçük Menderes River forms a rich coastal wetland inside in the Selçuk plain. Three saline/brackish lakes, one swamp and Küçük Menderes River are these wetlands’ components. Alkaline-slightly alkaline type lakes are recharged from precipitation and karstic springs that discharge from marble-schist and marble-alluvium contacts in the northern and southern parts of the study area. Water types of the wetland are Na–Cl and Na–Ca–Mg–HCO₃–Cl in both rainy and dry seasons. Both seawater intrusion and evaporation, as being the sources of the ions, justify the presence of Na–Cl, Na–SO₄ and Cl–SO₄, in the wetland water. Environmental isotopes were used to identify the relationship between wetland and groundwater in the Selçuk plain. The δ¹⁸O and δD composition of wetland area samples have changed between ?6.42 to ?4.56‰, and ?36.40 to ?23.80‰, respectively. The lakes and rivers are plotted on the mixing line by slope of 5.2 and these data indicate that wetland is affected from seawater intrusion. The recharge area that was sampled in order to compare the wetland has Ca–HCO₃ water type with a neutral-slightly alkaline pH values and the main hydrogeochemical process is weathering the different types of silicates. Iron, manganese and selenium are the dominant minor ions due to the high biological activities and organic matters in the lakes. There are two contamination risks for this wetland: (1) waste disposal site and (2) water treatment plant where the purified waters are released into the river. EC, Al, As, Cd, Cu, Fe and Zn values exceed those of aquatic life standards. In the near future these sites will pose a danger for wetland wild life and surrounding irrigation water suppliers.     

黑龙江省扎龙湿地及其周边地区土壤碳储量估算与1986年以来的变化趋势研究

以黑龙江省扎龙湿地及其周边地区多目标区域地球化学调查、第2次土壤普查数据为基础,通过不同土地利用方式下土壤全碳、有机碳密度、储量的估算,研究该地区20a来土壤碳库的变化趋势。结果显示：扎龙沼泽湿地区0-100cm土体的有机碳密度约为37884t／km^2;当沼泽地退化为草地或围垦为耕地后,土壤中有机碳的损失率高达66．...     

Geochemistry of iron ochres and mine waters from Levant Mine,Cornwall

The geochemistry of metal-rich mine waters and mineral precipitates from the Levant mine, Cornwall, has been examined. Sulphide oxidation at Levant mine has produced a wide range of secondary sulphides, oxides, chlorides, sulphates and carbonates in a gossan environment. The mine waters display a wide variation in alkalinity, pH, chloride, sulphate, sodium, potassium and heavy metal content which can be explained by variable degrees of mixing between acidic, metal-rich, rock drainage waters and neutral to alkaline sea waters. Transition metals are soluble in the acidic mine waters with concentrations up to 665 mg/l Cu, 41 mg/l Zn, 76 mg/l Mn, 6 mg/l Co and >2500 mg/l total Fe. The production of acid rock drainage and leaching of metals can be related to sulphide oxidation. Where these metal-rich acidic waters mix with infiltrated sea water, neutralization occurs and some metals are precipitated (principally Cu). Where pools of mine drainage are stagnant native copper and cuprite are precipitated, frequently observed replacing iron pipes and rail tracks and wooden shaft supports, due to electrode potential differences. In these solutions, dissolved copper species are also reduced by interaction with wood-derived organic species. Precipitation of iron oxyhydroxides, caused by a pH increase, also occurs and leads. to coprecipitation of other metals, including Cd, Co, Ph, Mn, Ag and Zn, thus limiting the release of dissolved metals in solution from the mine. However, the release of suspended metal-rich ochres in mine discharge waters (with high Ph, Zn, Cd, Mn, Ni, Sn, Sb, As, Bi, Cu, Co and Ag) will still present a potential environmental hazard.     

Arsenic mobility in weathered gold mine tailings under a low-organic soil cover

Historical gold mining operations in Nova Scotia, Canada, resulted in numerous deposits of publicly accessible, arsenic (As)-rich mine waste that has weathered in situ for 75–150 years, resulting in a wide range of As-bearing secondary minerals. The geochemical heterogeneity of this mine waste creates a challenge for identifying a single remediation approach that will limit As mobility. A 30-cm-thick, low-organic content soil cover was evaluated in a laboratory leaching experiment where, to simulate natural conditions, the equivalent of 2 years of synthetic rainwater was leached through each column and two dry seasons were incorporated into the leaching protocol. Each column was a stratigraphic representation of the four major tailings types found at the historical Montague and Goldenville gold mine districts: hardpan tailings, oxic tailings, wetland tailings, and high Ca tailings. Hardpan tailings released acidic, As-rich waters (max 12 mg/L) under the soil cover but this acidity was buffered by surrounding oxic tailings. Leachate from the oxic tailings was circumneutral, with average As concentrations between 4.4 and 9.7 mg/L throughout the experiment. The presence of carbonates in the high Ca tailings resulted in near-neutral to weakly alkaline leachate pH values and average As concentrations between 2.1 and 6.1 mg/L. Oxidation of sulfides in the wetland tailings led to acidic leachate over time and a decrease in As concentrations to values that were generally less than 1 mg/L. This study shows that the use of a low-organic content soil cover does not create reducing conditions that would destabilize oxidized, As-bearing secondary phases in these tailings. However, oxygen penetration through the cover during dry seasons would continue to release As to tailings pore waters via sulfide oxidation reactions.     

不同温度、羧酸溶液中长石溶解模拟实验

报道了在100℃、140℃下微斜长石在不同羧酸溶液中的溶解实验数据。通过实验表明1)反应温度增高,可增强溶液中阳离子的活性和迁移性,加快长石溶解的反应速率,促进长石的溶解。2)在强酸性条件下,pH值的变化可影响长石的溶解。但在中等酸性条件下,pH值对长石的溶解影响很小。3)羧酸(乙二酸)可不同程度地促进长石溶解,可通过形成乙二酸络合物的形式,增加离子在溶液中的溶解度。但乙酸络合物的作用不明显。长石溶蚀导致岩石孔隙度变大,并且改善孔喉性质。同时,由于乙二酸络合物的存在,增加了Si在溶液中的溶解度,阻止了石英加大和其它成因SiO₂的生成,有利于次生孔隙和原生孔隙的保存。4)长石溶解使溶液中Al的浓度较高,但由于铝-羧酸络合物的亲油性比亲水性强,故有一部分Al被分配到油相中,这也是目前大多数油田水中Al浓度偏低的主要原因。     

“Rust” contamination of formation waters from producing wells

In the Alberta Basin there is a significant difference in the content of Fe between formation waters from drillstem tests and formation waters from producing wells. This was demonstrated using a data set comprising 525 formation waters from drillstem tests and 107 formation waters from producing wells. Both a cross-plot of Mn and Fe in the two sets of formation waters and box plots of the same data sets showed that formation waters from producing wells have dominantly Fe>Mn, compared with those from drillstem tests which are characterized by Mn>Fe. Suspecting that “rust” contamination from well casing and ancillary equipment was the cause, the pH values of the samples were compared to see if the two data sets also differed in pH. It was demonstrated that not only are formation waters from drillstem tests less acidic than those from producing wells, but there is a systematic statistical trend of increasing acidity with age of the strata (temperature, depth, and increased amounts of the acid gases — H₂S and CO₂). The difference between the pH of formation waters from drillstem tests and producing wells is attributed to the partial scrubbing of the acid gases from the fluids produced during the drillstem test; this results in less acidic formation waters. Vanadium may also be enhanced in formation waters from producing wells. This note reports these differences and cautions too much reliance on values for Fe in waters from producing wells.     

黄河湿地孟津段不同植物群落类型土壤有机质含量变化特征研究

通过对黄河湿地孟津段不同湿地植被群落类型土壤进行采样分析,探讨了黄河小浪底水库修建之后调水调沙对下游滨河湿地不同植被群落类型土壤沉积特征的影响,并系统研究了滨河湿地土壤有机质的空间分异特征。研究结果表明：受上游小浪底水库建设的影响,滨河湿地不同植被群落类型土壤沉积层次和沉积厚度变化较大,近岸湿地植被向陆生演替的特征明显,土壤沉积加速、并不断向河道推移;滨河湿地不同植物群落类型、不同土壤层次的土壤有机质含量差异显著;典型湿地特征的植被群落表层土壤有机质含量明显高于其它深部沉积土壤;滨河湿地土壤有机质含量的显著差异性和受外部条件的显著控制作用,充分反映了滨河湿地生态系统的脆弱性。     

Effects of groundwater extraction from crystalline hard rock on water chemistry in an acid forested catchment at Gårdsjön,Sweden

Atmospheric deposition of S in Sweden has decreased by some 80% over the last 15 a, resulting in a general reduction of SO₄ concentrations in ground and surface water. This project, however, shows that artificial hydrological alteration in an acid wetland can reverse this trend and increase acidity and SO₄ concentrations. The experiment involved the monitoring of two catchments in relatively virgin conditions. In one of the catchments, an experiment with intensive groundwater extraction from the bedrock was carried out. During the experiment, the runoff from the catchment decreased by 50%. Furthermore, the extraction of groundwater resulted in increased seasonal aeration of the centrally located wetland, leading to oxidation of reduced S bound to the soil layers of the wetland. The S changed to solute SO₄, with a subsequent SO₄ surge. Thus, the experiment resulted in an induced acidification of the wetland and runoff waters. The extraction of groundwater significantly increased the recharge of water from the overburden, glacial till and organic soils to groundwater in the bedrock, which in turn reduced the retention time in the bedrock aquifer. These changes resulted in the chemical signature of the groundwater in the bedrock becoming similar to those of the wetland. The findings revealed deterioration in the water quality in the bedrock due to increased concentrations of dissolved organic C and SO₄, as well as a decrease in pH.     

Organic matter in ground- and surface waters in the area of the Annenskii geothermal field,Russian Far East

The paper presents author’s data on the composition of water-soluble organic matter in thermal, cold groundwaters, and surface waters in the Annenskii geothermal field. The waters contain 75 organic compounds of 13 homologous series, with 72 of these compounds identified in the thermal waters. The compounds are mostly of biogenic origin. Organic matter in the thermal waters differs from that in the cold groundwaters in containing nitrogen-bearing compounds, isoalkanes and alkenes. The compositional specifics of the saturated hydrocarbons suggests their partly abiogenic origin.     

湿地固碳效果研究——以黑龙江省扎龙湿地为例

依据多目标区域地球化学调查成果,以扎龙湿地为对象,根据表层（0~20 cm）土壤与深层（150~200 cm）土壤样品有机碳含量分析结果,计算了研究区有机碳单位储量,研究了湿地土壤中有机碳的含量分布和变化特征,比较了不同土地利用方式间的土壤有机碳储量的差异,对比了20年来湿地土壤中有机碳储量的变化.结果显示湿地土壤中有机碳处于增加状态,说明湿地是“碳汇区”.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

吉林省西部湿地土地利用格局变化的多情景模拟

吉林省西部属于生态脆弱区,湿地作为重要的生态单元,其发展变化对区域生态环境产生重要影响。近年来,由于受到较多的人为干扰,该区域湿地变化极为显著。为了充分发挥湿地生态环境功能,促进区域生态环境改善,以吉林省西部2000-2010年湿地变化数据为基础,基于情景分析法设置了自然变化（情景1）、规划优先（情景2）和生态优先（情景3）三种情景,利用CLUE-S模型对2020年湿地空间格局进行模拟,并从湿地空间分布变化特征和景观抗干扰能力两个方面对不同情景下的湿地格局进行分析评价,旨在了解不同情景下湿地格局的差异性,寻求合理的湿地空间分布格局。结果表明：CLUE-S模型的土地利用预测正确率为84.54%,κ指数为0.83,能够较好地模拟2020年湿地格局变化,特别是对沼泽湿地、水域和建设用地模拟效果较好;不同情景下湿地空间格局特征具有明显的差异性,三种情景下的沼泽湿地的质心均偏向西南,水域的质心均偏向东南,而水田的质心在情景1中偏向东北,在情景2和情景3中偏南,沼泽湿地和水田在情景3比情景1中具有更强的聚集性,而水域恰相反,情景1比情景3中具有更强的聚集性;不同情景下的湿地景观抗干扰能力不同,2010-2020年,情景1中的所有湿地类型的景观干扰指数都逐渐增加,而情景2和情景3中沼泽湿地和水域的景观干扰指数逐渐降低,尤以生态优先情景的下降幅度最大。表明在实施科学的生态建设时,湿地景观具有较强的抗干扰能力。     

Gold Content in Siliceous Deposits Formed from Acidic and Iron-rich Geothermal Waters at Hatchobaru, Central Kyushu, Japan

Abstract: The gold content in siliceous deposits formed from geothermal waters at the Hatchobaru geothermal power station in central Kyushu, Japan, was determined by inductively coupled plasma quadrupole mass spectrometry (ICP–MS). It ranges from 1.3 to 4.6 mg/kg. The highest gold content was obtained from the siliceous deposit formed from acidic waters. In this siliceous deposit, hydrous iron(III) oxide of amorphous state is a major constituent, suggesting that hydrous iron(III) oxide might play an important role when gold is concentrated into siliceous deposits formed from acidic and iron-rich geothermal waters.     

A compound-specific n-alkane δC and δD approach for assessing source and delivery processes of terrestrial organic matter within a forested watershed in northern Japan

We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ¹³C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ¹³C values of odd carbon numbered C₂₃-C₃₃n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ¹³C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C₂₅-C₃₁n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.     

Pore water geochemistry near the sediment-water interface of a zoned, freshwater wetland in the southeastern United States

 Sediment and its associated pore water were collected from a zoned, freshwater, riparian wetland, located in the Talladega National Forest, northeastern Hale County, Alabama, to study the porewater chemistry and its spatial changes within and between the wetland ecological zones. Obvious changes in pH, Eh and element concentrations were observed between the different wetland ecological zones. Major cations (Ca, Mg, and Na) and trace elements (B, Ba, Sr, and Mn) have very good spatial correlation with Fe and Mn distributions, both in the pore water and the sediment, suggesting that adsorption on, and desorption from, iron and manganese oxyhydroxides are important processes controlling the distributions of these elements in the wetland sediment. However, an equilibrium adsorption model is not able to explain the distribution of trace elements between the pore water and sediment. A redox kinetic model gives similar vertical profiles for iron and the correlated elements as those measured in the field and thus suggests that the relative rates of ferrous iron oxidation and the reductive dissolution of ferric iron in the sediment are important variables determining the distributions of these elements in the wetland pore waters. Received: 31 October 1996 · Accepted: 27 May 1997