Epikarst hydrology and implications for stalagmite capture of climate changes at Grotta di Ernesto (NE Italy): results from long‐term monitoring

Grotta di Ernesto is a cave site well suited for palaeoclimate studies because it contains annually laminated stalagmites and was monitored from 1995 to the end of 2008 for microclimate, hydrology and hydrochemistry. Long‐term monitoring highlighted that cave drips show three different hydrological responses to rainfall and infiltration: (1) fast seasonal drips in the upper part of the cave, which are mostly fed by fractures, (2) slow seasonal drips, located at mid‐depth in the cave characterized by mixed feeding and (3) slow drips, mostly located in the deeper gallery, which are fed by seepage flow from bulk porosity with a minor fracture‐fed component. The slow drips display daily cycles during spring thaw. Monitoring also indicated that drip waters are only slightly modified by degassing within the soil zone and aquifer and by prior calcite precipitation. Hydrochemical studies show a clear seasonality in calcite saturation index, which results in most cave calcite precipitation occurring during late autumn and winter with similar amounts of precipitated calcite on most stalagmites, regardless of drip rate (discharge) differences. Drip rate, and drip rate variability, therefore, has a minor role in modulating the amount of annual calcite formation. In contrast, drip rate, when associated with moderate reduction in calcite saturation index, clearly influences stalagmite morphology. Increasing drip rate yields a passage from candle‐, to cone‐ to dome‐shaped stalagmites. Very high drip rates feed speleothems with flowstone morphology. In summary, monitoring provides information about the karst aquifer and how hydrology influences those physical and chemical characteristics of speleothems which are commonly used as climate proxies. Copyright © 2010 John Wiley & Sons, Ltd.     

Temporal variation in properties of an uncropped,ploughed Miamian soil in relation to seasonal erodibility

Knowledge of seasonal variation in soil structural and related properties is important for the determination of critical periods during which soil is susceptible to accelerated erosion and other degradative processes. The purpose of this research was to evaluate the magnitude of seasonal variations in selected soil and deposited sediment properties in relation to soil erodibility for a Miamian silt-loam soil (Typic Hapludalf) in central Ohio. Erosion plots (USLE-type) were established on a 4·5% slope and maintained under bare, ploughed conditions from 1988 to 1991. Particle size distribution, bulk density(ρ_b), percentage water stable aggregates (WSA), soil organic carbon (SOC), and total soil nitrogen (TSN) of both soil and sediment samples were monitored between Autumn 1989 and Spring 1991. The soil and sediment particle size distributions followed no clear seasonal trends. Soil ρ_b increased following tillage (1·20 Mg m⁻³) and was highest (1·45 Mg m⁻³) during the autumn owing to soil slumping and consolidation upon drying. Low winter and spring values of ρ_b and %WSA (20–50% lower than in autumn) were attributed to excessive wetness and freeze–thaw effects. Both SOC and soil TSN contents progressively declined (from 2·18 to 1·79% and 1·97 to 1·75 g kg⁻¹, respectively) after ploughing owing to maintenance of plots under bare, fallow conditions. Spring highs and autumn lows of sediment SOC (3·12 vs. 2·44%) and TSN (2·70 vs. 1·96 g kg⁻¹) contents were a result of the combined effects of soil microbial activity and rainfall erosivity. Soil properties such as bulk density, SOC and WSA, which vary seasonally, can potentially serve as predictors of seasonal soil erodibility, which, in turn, could improve the predictive capacity of soil erosion prediction models. © 1998 John Wiley & Sons, Ltd.     

The regime of dissolved gases and organic matter in Selenga basin rivers

The gas regime and active reaction of water in Selenga basin rivers are analyzed. It is shown that, in the lower reaches of the Selenga and Uda rivers, which experience the highest anthropogenic impact, the minimal values of hydrogen index were recorded in under-ice period, while in the rivers of Chikoi, Khilok, Dzhida, and Temnik, during spring flood and summer freshets. The concentrations of organic substances are heterogeneous and vary widely under the effect of matter input with major tributaries and wastewater discharge from GOS. It has been established that the concentrations of readily oxidizable organic substances in 28–33% of the taken samples are above the established standards on maximal allowable concentrations in the period of open river channels. In spring and autumn, the organic matter in the rivers of the basin is mostly represented by soil terrigenous material.     

Fluorescence of dissolved organic matter as a natural tracer of ground water

The fluorescence properties of dissolved organic matter (DOM) in ground water in the Permian limestone of northeast England is determined from six monitoring boreholes, a private water supply well and from a natural resurgence in a flooded collapse doline in the environs of Darlington, County Durham, northeast England. Measurements of both protein and "fulvic-like" fluorescence was undertaken from January to December 1999. The wavelengths of fulvic-like fluorescence excitation and emission and of protein fluorescence emission were all determined to be sensitive fingerprints of organic matter fluxes through the ground water, with water within the till and within both gypsum and limestone strata deep inside the Magnesian Limestone being differentiated by these parameters. Previous research has suggested that proteins in waters are "young" in age, hence our seasonal variations suggest that we are sampling recently formed DOM. The rapid response of all deep borehole samples suggests relatively rapid ground water flow, probably through karstic cave systems developed in the gypsum and solution widened features in the dolomitic limestone. Our results suggest that use of both protein and fulvic-like fluorescence wavelength variations provides a DOM signature that can be used as a natural tracer.     

Study of Heavy Metal Compound Transformations in Surface Waters

Results of studying Fe(III) hydrolysis and sorption of heavy metal compounds by organic matter of bottom sediments are discussed. The rate of Fe(III) hydrolysis is found to be largely determined by the concentration of dissolved organic substances. Values of kinetic parameters are obtained for heavy metal compounds sorption under static and dynamic conditions. Calculating the solubility of Fe, Cu, Cd, Zn, and Pb sulfides allowed the assessment of the amount of metals lost by bottom sediments due to the formation of metal complexes with dissolved organic substances contained in natural waters.     

Seasonal isotopic variability of precipitation and cave drip water at Indian Oven Cave,New York

A major assumption in palaeoclimatic studies using speleothems is that cave‐seepage waters are homogenized as they pass through the bedrock, so that they record the average annual isotopic signal of precipitation. A year‐long study during 2001–02 was conducted at Indian Oven Cave in eastern New York State, USA, to investigate how cave‐seepage water isotopic signals relate to those of precipitation. Samples were collected biweekly and analysed for stable isotopes of oxygen and hydrogen. Our study shows that, for this cave, homogenization did not occur, as seepage waters had the same seasonal variability as precipitation. However, mean seepage water isotopic values were very close to those of the mean values for precipitation. Rapid flow‐through times of seepage water show that the speleothems can record climate conditions above the cave contemporaneously. At one location, flow ceased during the winter; therefore, isotopes measured in cave drip waters reflected only the enriched summer isotopes. Under certain circumstances, the analysis of calcite sampled from those drip waters may then lead to a false conclusion of a warming during that period, instead of the fact that it was merely a drier winter period. Copyright © 2005 John Wiley & Sons, Ltd.     

Isotopic offsets in throughfall and stemflow may have small effects on estimates of winter precipitation fractions

Forest canopies alter the amount and isotopic composition of precipitation reaching the forest floor. Thus retention, evaporation and transport processes in forest canopies, and their effects on water isotopes, are key to understanding forest water cycling. Using a two-year isotope dataset from a mixed beech/spruce forest in Zurich, Switzerland, we assessed the isotopic offsets between precipitation, throughfall and stemflow. We also analysed how these offsets affect estimates of the fraction of soil water that is derived from winter precipitation. Throughfall was typically enriched in heavy isotopes compared to precipitation, but isotopically lighter than stemflow, with average δ²H of −64.3 ‰, −59.9 ‰ and − 56.3 ‰ in precipitation, throughfall and stemflow, respectively. The differences between beech and spruce were rather small compared to the seasonal differences in precipitation isotopes. Isotopic offsets between precipitation and throughfall/stemflow were smaller during the spring and summer months (March through August) than during fall and winter (September through February). Bulk and mobile soil waters at 10 and 40 cm showed smaller seasonal variations than those in precipitation, throughfall and stemflow, and were isotopically lighter than recent precipitation, with the largest offsets occurring during the summer months (June through August) for bulk soil waters. Thus, bulk soil waters at both depths contain a mixture of precipitation from previous events and seasons, with over-representation of isotopically lighter winter precipitation. Mobile soil waters were more similar to recent precipitation than bulk soil waters were. Throughfall isotopes were slightly heavier than precipitation isotopes, resulting in different sinusoidal fits for seasonal isotopic cycles in precipitation and throughfall. These differences lead to small underestimates in the fraction of soil water originating from winter precipitation, when open-field precipitation rather than throughfall is used as the input data. Together our results highlight the importance of isotope measurements in throughfall and stemflow for the assessment of precipitation seasonality and water cycling across forested landscapes.     

The Analysis of the Seasonal,Spatial, and Compositional Distribution of Humic Substances in a Subtropical Shallow Lake

The spatial and temporal distribution of humic substances in aquatic ecosystems can have important effects on ecosystem productivity, negatively impacting primary productivity while positively impacting secondary productivity. In the present investigation, a large shallow lake ecosystem was studied to determine the spatial and seasonal variation of the composition and concentration of humic substances. Concentrations of total dissolved organic matter, humic acid, and fulvic acid were found to display significant spatial distributions (1.3…13.5 mg/L, DOM; 0.1…5.4 mg/L, HA). The distribution is described by using mapping techniques and the analysis of the spatial distribution of the lake. An analysis of the seasonal variations also indicated the dependence of the occurrence of these compounds on meteorological and hydrological conditions. To identify the potential sources of these organic materials, an analysis was made of the ratio of humic and fulvic acid fractions and total DOM. It was found that areas of high DOM concentration coincided with the areas of highest HA percentage of total DOM. Furthermore using the ratio of the normalised concentrations of HA, FA, and residual DOM (< 5000 g/mol) it was found that areas dominated by each are spatially distinct. This confirms the hypothesis that in these shallow lakes, photodegradation and bacterioplankton activity will create a residence time dependent zonation of each component of the total DOM.     

Role of Humification Processes in Recycling Organic Wastes of Various Nature and Sources as Soil Amendments

Recycling the large amounts of organic wastes produced by agriculture, forestry, urban and industrial activities as soil, organic amendments are the most popular and efficient option for avoiding their dispersion in the environment and restoring, maintaining, and/or improving the content of soil organic matter. Chemical stability and biological maturity are two important factors for the successful use of organic wastes in agriculture with limited risk for the surrounding environment. Stabilization and maturation of raw organic wastes inherently imply the achievement of an extensive humification, that is, a wide conversion of easily degradable organic matter to refractory organic compounds that resemble native soil humic substances (HS). Soil HS are the most important components of soil organic matter responsible of several soil functions and processes. As a consequence, the amount and quality of HS‐like fractions in any organic amendment are believed to be of primary importance for its agronomic efficacy, environmental safety and economic value. The first part of this review focuses on the chemical and physico‐chemical changes occurring in the humic substances (HS) ‐like fractions of organic wastes of various nature and sources subjected to common treatment processes aimed at producing environmentally‐safe soil amendments with beneficial agronomic properties. The second part discusses the composition, structure, and chemical reactivity of the HS‐like components in organic amendments of various origins and nature, and their effects on native soil HS. The review concludes by highlighting the need for innovative research targeted mainly to achieve a better fundamental understanding of the molecular structure and reactivity of soil HS and HS‐like fractions in organic amendments, the mechanisms of HS formation and transformations in the natural environment and during the treatment processes of raw organic wastes, the interactions with metals and organic xenobiotics, and the direct physiological effects that HS may exert on plants.     

Coccolithophores in the upwelling waters of Portugal: Four years of weekly distribution in Lisbon bay

From July 2001 to May 2005, seawater samples were collected once a week at a fixed station in Lisbon bay (38°41′N, 09°24′W) in order to describe the ecological dynamics of the coccolithophore community. The seasonal and interannual distribution patterns of the different species and their relationships with environmental parameters are addressed. The present work aimed to identify potential proxies for different local water bodies and environmental conditions. Throughout the period of study, the upwelling events were weak and progressively more persistent. High sea surface temperatures (SST) were observed earlier in the year; summers and winters were gradually warmer and colder, respectively. Salinity variations reflected the different weather conditions as they are strongly influenced by rainfall and thus by the Tagus river flow. The extended periods of weak upwelling and the overall increase in SST resulted in the development of phytoplankton populations as measured by chlorophyll a. However, the persistence of the upwelling, and thus shorter convergence periods, favoured other phytoplankton groups than coccolithophore populations as these decreased towards the end of the sampling period. The annual structure of the coccolithophore assemblage showed a pronounced and recurrent seasonal variability, mainly related with the intensity and persistence of upwelling. The highest cell densities were recorded from spring to autumn. An overall preference by most species for mature upwelled waters and low turbulent conditions was observed associated with high temperatures and salinities, although the species develop in different windows with mismatching maxima. The coccolithophores observed were capable of withstanding coastal processes such as turbulence and were well adapted to an environment rich in nutrients provided by both continental runoff and upwelling.The consistency of the results enabled local oceanographic tracers to be defined. Emiliania huxleyi and Gephyrocapsa species can be used as proxies of surface productivity waters during spring and summer while Coccolithus pelagicus indicates the presence of upwelling fronts. Calcidiscus leptoporus is a tracer of the convergence of subtropical oceanic waters onto the shelf, during winter while Coronosphaera mediterranea, Syracosphaera pulchra, Helicosphaera carteri and Rhabdosphaera clavigera revealed the presence of those waters during the short period that characterized the transition from upwelling to downwelling seasons.     

我国南方桉树人工林区水体泛黑物质分子组成及形成机理

我国南方桉树人工林区水库在秋冬季频繁出现黑水现象。现有研究指出,桉树叶中单宁酸等物质与金属离子(如铁离子)反应产生的金属-有机质络合物是导致这一现象的主要原因。然而,目前对于桉树叶中能形成金属-有机质络合物的潜在有机质前体物认识仍然有限,基于分子组成层面的桉树人工林区水库水体泛黑形成机理也尚不清楚。为此,本研究利用傅立叶变换离子回旋共振质谱(FT-ICR MS)等手段,对桉树叶浸泡液与典型桉树林区水库(金窝水库和天雹水库)水体中可溶性有机物进行了分子组成的分析。研究结果显示,桉树叶浸泡液主要由以苯三酚、没食子酸为母体的多酚类化合物及其多聚衍生物构成,其中最典型的化合物是鞣花酸(C₁₄H₆O₈)。冬季水库水中鞣花酸强度远高于夏季,且表层水体高于底层水体,这表明秋冬季大量凋落的桉树叶释放出的这些芳香多酚类物质会显著促进水库黑水的形成。进一步的实验证明,鞣花酸、苯三酚和没食子酸都会与铁离子发生络合反应,生成黑色沉淀。这些结果均表明,桉树叶溶解出的芳香多酚类物质是导致水库变黑的核心因素。本研究基于分子组成层面提出了桉树人工林区水库水体泛黑形成机理,对于桉树人工林区的黑水治理和保障水库饮用水安全具有十分重要的意义。     

The distribution of dissolved lead in the coastal waters of the East China Sea

The distribution of dissolved lead in the coastal waters of the East China Sea was investigated seasonally. The average concentrations in surface waters during the spring and autumn were 0.52 nM and 0.27 nM, respectively. In the spring, the concentration of dissolved Pb in the surface waters and bottom waters ranged from 0.13 to 1.86 nM and from 0.15 to 0.94 nM, respectively. For both the surface water and the bottom water, the highest values were observed at the Yangtze River Estuary. Seasonal variability of D-Pb between spring and autumn in the ECS was observed. These results suggested that riverine inputs and atmospheric inputs may be the main sources of lead in this area, while adsorption and co-precipitation on suspended particles at the river estuary and biological process may be the major sinks.     

Probleme der Wasserkontamination und ihrer analytischen Erfassung

The increasing loading of raw water for the drinking water supply with trace substances results in an increasing exposure of the population to toxicologically suspect substances. At present, the quality of such raw waters is evaluated mainly by cumulative parameters or individual substances with low eco- or humantoxicological relevance. Now, about 5 · 10⁵ environment-relevant organic substances must be taken into account, the number of individual compounds for a loaded receiving water being estimated to be 10³. Secondary contaminations are caused by oxidative processes of water treatment. In the trace substance analysis so far only about 40% of the organic substances are isolable by comparatively simple methods. From this derives the demand for developing standardized methods for determining cumulative and group parameters with a high value of information and indication, as e. g. organically bonded chlorine or halogens.     

Mechanisms controlling the intra-annual mesoscale variability of SST and SPM in the southern North Sea

Thermal and optical remote sensing data were used to investigate the spatial and temporal distribution of sea surface temperature (SST) and of suspended particulate matter (SPM) in the southern North Sea. Monthly SST composites showed pronounced seasonal warming of the southern North Sea and delineated the English coastal and continental coastal waters. The East-Anglia Plume is the dominant feature of the English coastal waters in the winter and autumn SPM composites, and the Rhine region of freshwater influence (ROFI), including the Flemish Banks, is the dominant feature of the continental waters. These mesoscale spatial structures are also influenced by the evolution of fronts, such as the seasonal front separating well-mixed water in the southern Bight, from the seasonally stratified central North Sea waters. A harmonic analysis of the SST and SPM images showed pronounced seasonal variability, as well as spring-neap variations in the level of tidal mixing in the East Anglia Plume, the Rhine ROFI and central North Sea. The harmonic analysis indicates the important role played by the local meteorology and tides in governing the SST and near-surface SPM concentrations in the southern North Sea. In the summer, thermal stratification affects the visibility of SPM to satellite sensors in the waters to the north of the Flamborough and Frisian Fronts. Haline stratification plays an important role in the visibility of SPM in the Rhine ROFI throughout the year. When stratified, both regions typically exhibit low surface SPM values. A numerical model study, together with the harmonic analysis, highlights the importance of tides and waves in controlling the stratification in the southern North Sea and hence the visibility of SPM.     

新疆博斯腾湖水体颗粒和溶解有机碳的季节变化及其来源初探

在博斯腾湖选取了13个点位,于2012年5、8、10月测定表层和底层水体中的颗粒有机碳、溶解有机碳、颗粒有机氮和叶绿素a含量.结果显示颗粒和溶解有机碳在表层水体中的浓度与底层相近.博斯腾湖水体中颗粒有机碳的季节变化十分明显,其平均浓度从春季(0.64 mg/L)到夏季(0.71 mg/L)变化不大,但在秋季变化十分显著(浓度达1.58 mg/L).其中西北湖区和湖心区颗粒有机碳的季节变化最明显,东部湖区颗粒有机碳的季节变化相对较小.博斯腾湖水体的颗粒有机碳在春、秋两季主要来自外源输入,在夏季受水体中浮游生物的影响较大.博斯腾湖水体中溶解有机碳也具有一定的季节变化,夏季浓度(平均为9.3 mg/L)略低于春、秋两季(平均为10.3 mg/L).溶解有机碳在河口区的季节变化最强,其夏季浓度明显偏低,主要是由于开都河河水的稀释作用.总体上,博斯腾湖水体中溶解有机碳浓度的变化主要受外部因素的影响.     

Alkaline Phosphatase Activity and Utilization of Dissolved Organic Phosphorus by Algae in Subtropical Coastal Waters

Alkaline phosphatase activity (APA) and the availability of dissolved organic phosphorus (DOP) to marine algae were determined in Xiamen Bay and in algal batch culture systems. Results showed that APA changed with seasons, increasing to the highest value in summer and decreasing to the lowest in autumn and spring in Xiamen Bay. Tests on natural populations of planktonic algae and bacteria community showed that algae were mostly responsible for DOP utilization, while bacteria could not take up DOP compounds. Results from algal batch cultures also supported the above conclusion. Relationships between APA and environmental factors indicated that APA was negatively correlated with phosphorus level such as phosphate and small molecular DOP, and APA played an important role in utilization of DOP by algae. All the results emphasized the ecological significance of DOP in subtropical coastal waters.     

Kinetic processes and stable isotopes in cave dripwaters as indicators of winter severity

We examine how the stable isotope composition of meteoric water is transmitted through soil and epikarst to dripwaters in a cave in western Romania. δ²H and δ¹⁸O in precipitation at this site are influenced by temperature and moisture sources (Atlantic and Mediterranean), with lower δ¹⁸O in winter and higher in summer. The stable isotope composition of cave dripwaters mimics this seasonal pattern of low and high δ¹⁸O, but the onset and end of freezing conditions in the winter season are marked by sharp transitions in the isotopic signature of cave dripwaters of approximately 1 ‰. We interpret these shifts as the result of kinetic isotopic fractionation during the transition phase from water to ice at the onset of freezing conditions and the input of meltwater to the cave at the beginning of the spring season. This process is captured in dripwaters and therefore speleothems from Ur?ilor Cave, which grew under such dripping points, may have the potential to record past changes in the severity of winters. Similar isotopic changes in dripwaters driven by freeze–thaw processes can affect other caves in areas with winter snow cover, and cave monitoring during such changes is essential in linking the isotopic variability in dripwaters and speleothems to surface climate.     

The Concentrations of Cadmium,Lead and Copper in Filtrated Baltic Sea Water Samples Collected at Two Seasons in 1969

Two research cruises on the Baltic Sea, in July and November of 1979, were made for investigating the Baltic Sea water for its contents of dissolved cadmium, lead and copper. Atomic absorption spectrophotometry and voltammetry were used as methods of investigation, the latter method having supplied slightly lower results. In the water layer of 0 … 50 m the cadmium concentrations were 0.03 … 0.05 μg/l and the lead concentrations were 0.1 … 0.2 μg/l, seasonal changes did not have any effect on them. The copper concentrations, on the other hand, were 0.4 … 1.2 μg/l in summer and 0.1 … 0.7 μg/l in autumn. Compared with ocean waters, the lead content is remarkably high. In anoxic deep waters of the Baltic Sea the concentrations of the three metals, especially that of cadmium, are very low (< 0.01 μg/l).     

Temporal and spatial variations in the discharge and dissolved organic carbon of drip waters in Beijing Shihua Cave,China

To detect the causal relationship between cave drip waters and stalagmite laminae, which have been used as a climate change proxy, three drip sites in Beijing Shihua Cave were monitored for discharge and dissolved organic carbon (DOC). Drip discharges and DOC were determined at 0 to 14‐day intervals over the period 2004–2006. Drip discharges show two types of response to surface precipitation variations: (1) a rapid response; and (2) a time‐lagged response. Intra‐annual variability in drip discharge is significantly higher than inter‐annual variability. The content of DOC in all drip waters varies inter‐ and intra‐annually and has good correlation with drip water discharge at the rapid response sites. High DOC was observed in July and August in the three years observed. The flushing of soil organic matter is dependent upon the intensity of rain events. The DOC content of drip water increases sharply above a threshold rainfall intensity (>50 mm d^?1) and shows several pulses corresponding with intense rain events (>25 mm d^?1). The DOC content was lower and less variable during the dry period than during the rainy period. The shape of DOC peak also varies from year to year as it is influenced by the intensity and frequency of rainfall. The different drip sites show marked differences in DOC response, which are dominated by hydrological behaviour linked to the recharge of the soil and karst micro‐fissure/porosity network. The results explain why not all stalagmite laminae are consistent with climate changes and suggest that the structure of the rainy season events could be preserved in speleothems. Copyright © 2008 John Wiley & Sons, Ltd.     

Zur Bewertung der Analytik und Interpretation des Gruppenparameters “Extrahierbares organisch gebundenes Halogen” von Wässern

Organohalogen compounds are gaining in importance in the control of surface and drinking water due to their unwholesome properties. An accumulation of the organohalogen compounds, occurring mostly at low concentrations, is possible in different ways. The author discusses the possibility and problems of the extractability from waters with the aid of organic solvents. The group parameter EOX that can be determined does not allow any statement concerning components of individual substances, but gives some clues to the state of surface and drinking waters which are mostly anthropogenically polluted. Results of practical examples as well as theoretical considerations indicate the importance of the different distribution coefficients in the solvent/water extraction system. The degree of extraction can be considerably increased by the application of suitable mixtures of solvents. In waters with a known composition, the probably detectable EOX-quantity can be calculated by means of theoretical degrees of extraction.