近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.     

Spatial Variation in the Optical Properties of Dissolved Organic Matter (DOM) in Lakes on the Canadian Precambrian Shield and Links to Watershed Characteristics

In the present study, we explored the use of various optical parameters to detect differences in the composition of the dissolved organic matter (DOM) in a set of lakes that are all located on the Canadian Precambrian Shield, but within which Cu and Ni speciation predictions were previously shown to diverge from measured values in some lakes but not in others. Water samples were collected with in situ diffusion samplers in 2007 (N = 18 lakes) and 2008 (N = 8 lakes). Significant differences in DOM quality were identified between the sampling regions (Rouyn-Noranda, Québec and Sudbury, Ontario) and among lakes, based on dissolved organic carbon concentrations ([DOC]), specific UV absorbance (SUVA₂₅₄), fluorescence indices (FI), and excitation–emission matrix (EEM) fluorescence measurements. Parallel factor analysis (PARAFAC) of the EEM spectra revealed four components, two of which (C3, oxidized quinone fluorophore of allochthonous origin, and C4, tryptophan-like protein fluorescence of autochthonous origin) showed the greatest inter-regional variation. The inter-lake differences in DOM quality were consistent with the regional watershed characteristics as determined from satellite imagery (e.g., watershed-to-lake surface area ratios and relative percentages of surface water, rock outcrops vegetative cover and urban development). Source apportionment plots, built upon PARAFAC components ratios calculated for our lakes, were used to discriminate among DOM sources and to compare them to sources identified in the literature. These results have implications for other areas of research, such as quantifying lake-to-lake variations in the influence of organic matter on the speciation of trace elements in natural aquatic environments.     

梅梁湾、大太湖夏季和冬季CDOM特征及可能来源分析

基于2004年夏季水华暴发期和冬季在梅梁湾及大太湖各2次采样,分析了夏季、冬季CDOM的特征及其可能的来源,发现夏季CDOM吸收系数、叶绿素a浓度均明显高于冬季,DOC浓度、CDOM吸收系数a(355)的变化范围分别为5.17～12.42 mg/L、2.57～6.77 m-1,最大值均出现在冬季(12月15日)的直湖港入湖口.CDOM吸收系数与DOC浓度、定标后的荧光值一般都存在显著正相关,但夏季由于受浮游植物降解的影响,与DOC浓度和荧光的相关性明显低于冬季.表征CDOM组成和来源的参数比吸收系数、M值、S值存在显著的季节差异,夏季吸收系数a*(355)值明显要大于冬季,而S值、M值则要小于冬季.夏季水华暴发时CDOM吸收系数与叶绿素a浓度空间分布较为一致,吸收系数与叶绿素a浓度存在正相关,浮游植物降解产物可能是水体中CDOM的重要来源;相反,冬季CDOM吸收系数呈现从梁溪河入湖口、湾内往湾口递减的趋势,其来源可能主要以陆源为主,受入湖河流的影响较大.     

Importance of CDOM Distribution and Photoreactivity in a Shallow Texas Estuary

This study examined freshwater discharge of dissolved organic matter (DOM) to the shallow Lavaca–Matagorda (LM) Bay estuarine system along the central Texas coast and investigated whether chromophoric DOM (CDOM) photochemical reactions have the potential to stimulate microbial activity within LM estuarine waters. Dissolved organic carbon (DOC) concentrations ranged from 3 to 10 mg C l⁻¹ and CDOM levels (reported as a ₃₀₅) ranged from 8 to 77 m⁻¹ during April and July, 2007, when the LM system was experiencing very high freshwater inputs. DOC and CDOM levels were well-correlated with salinities > 3, but exhibited considerable variability at salinities < 3. CDOM photobleaching rates (i.e., decrease in a ₃₀₅ resulting from exposure to solar radiation) for estuarine samples ranged from 0.014 to 0.021 h⁻¹, corresponding to photobleaching half-lives of 33–50 h. Our data indicate when Matagorda Bay waters photobleach; dissolved organic carbon utilization is enhanced perhaps due to enhanced microbial respiration of biologically labile photoproducts (BLPs). Net ecosystem metabolism calculations indicate that most of the LM system was net heterotrophic during our study. We estimate that BLP formation could support up to 20% of the daily microbial respiratory C demand in LM surface waters and combined with direct photochemical oxygen consumption could have an important influence on O₂ cycles in the LM system.     

Properties of fluorescent dissolved organic matter in the Gironde Estuary

The isolation, characterization and study of the properties of aquatic dissolved organic matter (DOM) still represent a challenge because of the heterogeneity, complexity and low concentration of organic material in natural waters. Based on its ability to interact with contaminants and thus to modify their transport and bioavailability, DOM is of interest for environmental purposes. The objective of this work was to better characterize DOM in the Gironde Estuary (southwestern France). The estuary represents an exchange zone between the continent and the Atlantic Ocean and conditions the transfer of organic and inorganic substances from the continental to the oceanic environment. Several samples were collected along the estuary during three cruises in 2002 and 2006. They were analysed using excitation–emission matrix (EEM) spectroscopy, a sensitive technique that allows direct analysis of water samples. Fluorescent DOM and dissolved organic carbon (DOC) did not behave conservatively in this estuarine system, i.e. the organic material did not undergo simple dilution from the upstream to the downstream part of the estuary. A seasonal variability in DOC content was pointed out, whereas few seasonal variations in DOM fluorescence were observed. DOM sources and processing in the estuary were further evaluated by determining two fluorescence indices – the humification index (HIX) and the index of recent autochthonous contribution (BIX). By applying these indices, the relative degree of humification (HIX) and autotrophic productivity (BIX) could be assessed. Based on the fluorescence and DOC results, the estuary was divided into three zones depending on salinity (S) and characterized by specific DOM: (i) A turbid zone of low salinity (S < 5) and high suspended particulate matter concentration with increase in the intensities of the α′ and α fluorophores, characteristic of humic-like compounds. (ii) A mid-estuarine zone (5 < S < 25) characterized by low autotrophic productivity and containing strongly degraded organic material, as shown by the low values of BIX and high values of HIX. (iii) A higher salinity area (S > 25) characterized by increased autotrophic productivity and a marked marine influence, and associated with high and low values of BIX and HIX, respectively. The HIX and BIX indices were shown as useful tools for readily defining and classifying DOM characteristics in estuarine waters.     

Compositional differences of chromophoric dissolved organic matter derived from phytoplankton and macrophytes

Chromophoric dissolved organic matter (CDOM) is an important component in the aquatic environment and plays a key role in light attenuation and in carbon biogeochemical cycles. We examined CDOM production in each of two laboratory experiments in which phytoplankton and macrophyte degradation were monitored using absorption and excitation–emission matrix fluorescence spectroscopy (EEMs). During the incubation period, CDOM was produced from phytoplankton and macrophytes, and partly decomposed by microorganisms. The absorption spectra of the phytoplankton derived and the macrophyte derived CDOM were distinct and characterized by peaks and shoulders in the UV bands. Production of CDOM absorption at 350 nm, a(350), was 0.0125 m²/g per unit of chlorophyll a from phytoplankton CDOM from 0–3 d. Meanwhile a(350) production was 2.708 × 10⁻⁴ m²/g per unit of wet biomass from macrophytes CDOM from 1–7 d. Despite the high production of CDOM by phytoplankton and macrophytes, extrapolation of these values to the field indicated that about 15% of total CDOM was produced from phytoplankton during algal blooms in Meiliang Bay in summer and about 8% of total CDOM was produced from macrophytes in the macrophyte dominated littorals. The mean value of the spectral slope (S) describing the exponential decrease of the absorption spectrum, which was strongly correlated to an optical index of molecular size, for the phytoplankton derived CDOM was 10.26 ± 2.05 μm⁻¹, which was significantly lower than the mean S of 14.47 ± 2.88 μm⁻¹ for the macrophyte derived CDOM (t-test, p < 0.001). The mean value of the spectral slope ratio (S_R) for the phytoplankton derived CDOM was 1.79 ± 0.52, which was significantly higher than that of 0.35 ± 0.58 for the macrophyte derived CDOM (t-test, p < 0.001). Three fluorescent components were validated in parallel factor analysis (PARAFAC) models calculated separately for phytoplankton derived and macrophyte derived CDOM, each CDOM source resulting in distinct excitation and emission maxima for each component. The significant differences in CDOM absorption spectra, S, S_R and PARAFAC fluorescence component characteristics, all showed that phytoplankton derived CDOM was compositionally distinct from macrophyte derived CDOM. Overall both sources were important to the CDOM pool in the shallow temperate lake.     

Application of excitation emission matrix fluorescence monitoring in the assessment of spatial and seasonal drivers of dissolved organic matter composition: Sources and physical disturbance controls

The environmental dynamics of dissolved organic matter (DOM) were characterized for a shallow, subtropical, seagrass-dominated estuarine bay, namely Florida Bay, USA. Large spatial and seasonal variations in DOM quantity and quality were assessed using dissolved organic C (DOC) measurements and spectrophotometric properties including excitation emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC). Surface water samples were collected monthly for 2 years across the bay. DOM characteristics were statistically different across the bay, and the bay was spatially characterized into four basins based on chemical characteristics of DOM as determined by EEM-PARAFAC. Differences between zones were explained based on hydrology, geomorphology, and primary productivity of the local seagrass community. In addition, potential disturbance effects from a very active hurricane season were identified. Although the overall seasonal patterns of DOM variations were not significantly affected on a bay-wide scale by this disturbance, enhanced freshwater delivery and associated P and DOM inputs (both quantity and quality) were suggested as potential drivers for the appearance of algal blooms in high impact areas. The application of EEM-PARAFAC proved to be ideally suited for studies requiring high sample throughput methods to assess spatial and temporal ecological drivers and to determine disturbance-induced impacts in aquatic ecosystems.     

Estimation of colored dissolved organic matter and salinity fields in case 2 waters using SeaWiFS: Examples from Florida Bay and Florida Shelf

Estimates of water quality variables such as chlorophylla concentration (Chl), colored dissolved organic matter (CDOM), or salinity from satellite sensors are of great interest to resource managers monitoring coastal regions such as the Florida Bay and the Florida Shelf. However, accurate estimates of these variables using standard ocean color algorithms have been difficult due to the complex nature of the light field in these environments. In this study, we process SeaWiFS satellite data using two recently developed algorithms; one for atmospheric correction and the other a semianalytic bio-optical algorithm and compare the results with standard SeaWiFS algorithms. Overall, the two algorithms produced more realistic estimates of Chl and CDOM distributions in Florida Shelf and Bay waters. Estimates of surface salinity were obtained from the CDOM absorption field assuming a conservative mixing behavior of these waters. A comparison of SeaWiFS-derived Chl and CDOM absorption with field measurements in the Florida Bay indicated that although well correlated, CDOM was underestimated, while Chl was overestimated. Bottom reflectance appeared to affect these estimates at the shallow central Bay stations during the winter. These results demonstrate the need for new bio-optical algorithms or tuning of the parameters used in the bio-optical algorithm for local conditions encountered in the Bay.     

Spatial-seasonal dynamics of chromophoric dissolved organic matter in Lake Taihu, a large eutrophic, shallow lake in China

From 2005 to 2009, the spatial distribution and the seasonal dynamics of chromophoric dissolved organic matter (CDOM) were explored in Lake Taihu in eastern China. The spatial-seasonal dynamics of CDOM absorption and three CDOM composition variables, including spectral slope (S), spectral slope ratio (S_R) and the M value, defined as the ratio of absorption at 250 nm/365 nm, were analyzed and discussed. Furthermore, river input processes and degradation of phytoplankton were studied to assess their impact on CDOM composition and the factors involved in the spatial-seasonal variability of CDOM. The CDOM absorption coefficient at a wavelength of 350 nm, a(350), ranged from 1.37-9.55 m⁻¹ with a mean of 3.33 ± 1.32 m⁻¹. Spatially, higher a(350) values, but lower spectral slope, spectral slope ratio and M values, were recorded in the northern algae dominated bays while lower values were recorded in southeastern macrophyte dominated bays. The a(350) was significantly higher in inshore waters than in offshore waters. Values of S, S_R and M decreased during the flood and algal bloom season in spring and summer whereas a(350) increased. In the three river profiles, the gradual decrease of a(350) along the trajectory from the river mouth into the lake during the flood season showed the contribution of allochthonous CDOM. A laboratory phytoplankton degradation experiment was conducted to determine the contribution of CDOM production from phytoplankton. The significant increase of a(350) with time in the CDOM production experiment underlines the importance of autochthonous CDOM production during the algal bloom season. In summary, the significant increase of a(350) in spring and summer (algal bloom season) may be due to both the allochthonous CDOM input from the surrounding rivers and the autochthonous production of CDOM from degrading phytoplankton.     

Cycling of trace metals (Mn, Fe, Mo, U, V, Cr) in deep pore waters of intertidal flat sediments

Trace metals (Mn, Fe, Mo, U, Cr, V) were studied in pore waters of an intertidal flat located in the German Wadden Sea. The study system is an example of a permeable tidal flat system where pore water exchange is affected by tidal driven pressure gradients besides diffusion. Permanently installed in situ samplers were used to extract pore waters down to 5 m depth throughout one year. The samplers were either located close to the tidal flat margin or in central parts of the tidal flat. Despite dynamic sedimentological and hydrological conditions, the general trends with depth in deep tidal flat pore waters are remarkably similar to those observed in deep sea environments. Rates of trace metal cycling must be comparably large in order to maintain the observed pore water profiles. Trace metals further show similar general trends with depth close to the margin and in central parts of the tidal flat. Seasonal sampling revealed that V and Cr vary concurrent with seasonal changes in dissolved organic carbon (DOC) concentration. This effect is most notable close to the tidal flat margin where sulphate, DOC, and nutrients vary with season down to some metres depth. Seasonal variations of Mn, Fe, Mo, and U are by contrast limited to the upper decimetres of the sediment. Their seasonal patterns depend on organic matter supply, redox stratification, and particulate matter deposited on sediment surfaces. Pore water sampling within one tidal cycle provides evidence for pore water advection in margin sediments. During low tide pore water flow towards the creekbank is generated by a hydraulic gradient suggesting that deep pore waters may be seeping out of creekbank sediments. Owing to the enrichment of specific elements like Mn in pore water compared to sea water, seeping pore waters may have an impact on the chemistry of the open water column. Mass balance calculations reveal that the impact of deep pore waters on the Mn budget in the open water column is below 4%. Mn deep pore water discharge of the whole Wadden Sea is estimated to be about 9% of the total dissolved riverine Mn input into the Southern North Sea.     

Marsh-water column interactions in two Louisiana estuaries. II. Nutrient dynamics

The exchange of dissolved nutrients between marshes and the inundating water column was measured using throughflow marsh flumes built, in two microtidal Louisiana estuaries: the Barataria Basin estuary and Fourleague Bay. The flumes were sampled between September 1986 and April 1988, coincident with an extended period of low sea level on the Louisiana coast. The Barataria Basin estuary is in the later, deteriorating stage of the deltaic cycle, characterized by low freshwater inputs and subsiding marshes. Both brackish and saline marshes supplied dissolved organic nitrogen (DON), inorganic nitrogen (ammonium + nitrate + nitrite = DIN), dissolved organic carbon (DOC), and total nitrogen (as total Kjeldahl nitrogen = TKN) to the water column. The export of DIN is probably related to the N accumulated in earlier stages of deltaic development and released as these marshes deteriorate. Coastal brackish marshes of Fourleague, Bay, part of an accreting marsh system in an early, developmental stage of the deltaic cycle, exported TKN to the open water estuary in all samplings. This marsh apparently acted as a short-term buffer of DIN by taking up NH₄ ⁺ in spring, when baywide concentrations were high, and supplying DIN to the estuary in summer and fall, when concentrations, in the bay were lower. Differences in phosphorus (P), DOC, and DON fluxes between these two estuaries were also observed. The Fourleague Bay site exported soluble reactive phosphorus (SRP) and total phosphorus (TP) and imported DOC. This P export may be related to remobilization of sediment-bound riverine P by the reducing, soils of the marshes. Fluxes of SRP at the Barataria Basin sites were variable and low while DOC was imported. Most imports of dissolved nutrients were correlated with higher upstream [source] concentrations, and flux rates were fairly consistent throughout the tide. Dissolved nutrient exports, did not correlate with upstream concentrations, though, and in many cases the flux was dominated by early, flood tide nutrient release. This pulsed behavior may be caused by rapid diffusion from the sediments early in the tidal cycle, when the sediment-water concentration gradient is largest. Interestuary differences were also seen in particulate organic matter fluxes, as the Fourleague Bay marsh exported POC and PON during all samplings while Barataria Basin imported these nutrients. In general, the magnitude and direction of nutrient exchanges in Louisiana marshes, seem to reflect the deltaic successional stage of the estuary.     

Adsorption characteristics of natural organic matter on activated carbons with different pore size distribution

The adsorption characteristics of natural organic matter (NOM) were investigated on the basis of fluorescence excitation emission matrix (EEM) by using four different coal-based activated carbons (ACs). For each AC, batch adsorption isotherms were analyzed using a modified Freundlich isotherm model on the basis of the fluorescence intensity of three major fluorescence peaks appeared in the fluorescence EEM reported to be reflective of the humic acid-like (P1), fulvic acid-like (P2) and aromatic protein-like (P3) substances, respectively, together with the well-used overall quality indices of dissolved organic carbon (DOC) and ultraviolet absorbance at the wavelength of 260 nm (UV260). It was found that, for all five quality indices, the adsorption capacity differed with the ACs used, and the modified Freundlich isotherm constant K estimated for P1, P2 and P3 was in close correlation with that of the total organic matter evaluated by DOC. Moreover, no matter which AC was concerned, the magnitude of the estimated K and the removal rate over a broader range of AC dose for P3 were apparently smaller than those for P1 and P2, suggesting the adsorbability of aromatic protein-like substances was lower than that of the humic acid-like and fulvic acid-like substances. The dependency of the adsorption capacity of NOM on the volume of pores in some specific size ranges of the ACs was also revealed.     

Species diversity and emergence patterns of nematocerous flies (Insecta: Diptera) from three coastal salt marshes in prince Edward Island, Canada

Emerging insects were monitored every 10 days between early May and late August 1993, from tidal pools in three coastal salt marshes on Prince Edward Island, Canada. The salt marsh pools ranged from about 1 m² to > 1,000 m² in surface area, and had salinities ranging from 11–27‰ Water temperatures through the study period ranged from 4–46°C. Most of the emerging insects were flies (Diptera; 85%), and two-thirds of these were in the sub-Order Nematocera, mainly Chironomidae, Ceratopogonidae, and Culicidae. Forty-three species of Nematocera were identified, although most of these were rare occurrences, and twelve of the species are undescribed. No consistent relationships were found between abundance or diversity and pool size or marsh for Nematocera species overall, although some species showed a statistical preference for a particular marsh or pool size. Emergence patterns were consistent between marshes for species found in different marshes, but overall patterns were highly variable, depending upon species.     

Dissolved organic matter fluorescence spectroscopy as a tool to estimate biological activity in a coastal zone submitted to anthropogenic inputs

Here we report on an investigation of the three-dimensional excitation-emission-matrix (EEM) fluorescence spectra of unconcentrated water samples collected in 1996, 1998 and 1999 at a site particularly propitious for macro-algae development. The degradation of these macro-algae was studied to determine the influence of their exudates on natural water EEM fluorescence spectra. This work demonstrates that biological activity is one of the major factors involved in the formation of the blue-shifted fluorescence band observed in marine waters (β component Ex/Em=310–320 nm/380–410 nm); our study also shows that fluorescence can be used to evaluate the biological activity both quantitatively and to determine its different phases.     

北京石花洞石笋微层层面有机物质的形成时间及机理初探

通过对北京石花洞滴水水溶性有机碳(DOC)近一个水文年的观测,发现不同点滴水DOC浓度均表现出明显的季节性变化,7月中旬均有一个大的主峰出现。初步说明中国北方石笋微层的层面物质沉积于7月雨季,主要来源于大的雨量对土壤中有机质的淋溶;洞穴顶板较薄的滴水点在5月和8月有明显的DOC次峰,可能与石笋亚年层形成有关。     

The distribution and stable carbon isotopic composition of dissolved organic carbon in estuaries

The distributions of dissolved organic carbon (DOC) and the natural carbon isotope ratio of DOC (DO¹³C) in estuaries reflect the predominant sources and sinks of organic matter from both allochthonous and autochthonous origins. The traditional view is that DOC in land-margin ecosystems reflects mainly the mixing of land-derived and oceanic DOC. However, this view is not consistent with the bulk of our data from a survey of DOC and DO¹³C distributions in estuaries on the East and Gulf coasts of the USA. While it is accurate that the DOC in estuaries includes material derived from land and from the ocean, the distributions of DOC and DO¹³C in several estuaries reflect additional DOC inputs from estuarine phytoplankton and tidal marshes. Even when DOC concentrations were distributed conservatively, the isotopic composition of the DOC revealed the existence of a dynamic cycle of DOC input and removal in some systems.     

Variability in dissolved organic matter fluorescence and reduced sulfur concentration in coastal marine and estuarine environments

Fluorescence characterization of dissolved organic matter (DOM) and measurements of Cr-reducible sulfide (CRS) are presented for 72 coastal marine and estuarine water samples obtained from the USA and Canada. Each sample is identified according to source: terrigenous, autochthonous, wastewater or mixed. Fluorescence data are resolved into contributions from humic, fulvic, tyrosine and tryptophan-like fluorophores. Humic and fulvic-like fluorophores correlate well with dissolved organic C (DOC) (r² = 0.73 and 0.71, respectively) but tyrosine and tryptophan-like fluorophores show no correlation with DOC. Quality factors are identified by normalization of fluorescence contributions to DOC. Humic and fulvic components show no statistical differences between sources but the amino acid-like fluorescence quality factors show significant variations between source, with highest values for autochthonous sources (0.07 ± 0.01 arbitrary fluorescence units per mg of C) versus low values (0.015 ± 0.005) for terrigenous source waters. CRS concentrations are highly variable from 0.07 ± 0.01 to 7703 ± 98 nM and do no correlate with DOC except when terrigenous source waters (n = 13) are separated out from the total sample set (r² = 0.55). There is an open question in the literature; does DOC source matter in terms of protective effects towards metal toxicity? Here is shown that DOC molecular-level quality does vary and that this variation is mostly in terms of the contributions of amino acids to total fluorescence.     

Seasonal Dynamics in Dissolved Organic Carbon Concentrations in a Coastal Water-Table Aquifer at the Forest-Marsh Interface

The seasonal dynamics of dissolved organic carbon (DOC) in a subterranean estuary were examined in a coastal water-table aquifer extending across a forest-marsh interface into an adjacent tidal creek that leads to North Inlet (SC). The aquifer is characterized by groundwater flow from the forest recharge area towards the creek. DOC concentrations range from 50 to 140 mg L^-1 in the shallow portions of the aquifer below the forest and undergo seasonal changes that are inversely related to temperature and precipitation conditions. Markedly lower DOC concentrations (<10 mg L^-1) in the deep portion of the aquifer are consistent with the loss of a large fraction of the original DOC along the groundwater flow paths. Mass balance estimates indicate that over 60% of the DOC losses are due to sorption reactions whereas the rest appear to be caused by heterotrophic decay. Groundwater DOC discharge from the forest, which occurs in a restricted zone of the high marsh, is 5.5 mg carbon m^-2 d^-1 and accounts for a minor component of the annual carbon export from North Inlet. In contrast, moderately saline (2–12 ppt) ground waters below the marsh display elevated DOC concentrations (20 mg L^-1) that appear to be the result of mixing of fresh ground waters and surface seawater during tidal seepage and concentration during evapotranspiration. The flux of DOC associated with the discharge of these saline ground waters is 600 mg carbon m^-2 d^-1, which represents a significant fraction of the annual DOC budget for North Inlet.     

A Comprehensive Study of Silica Pools and Fluxes in Wadden Sea Salt Marshes

As an essential nutrient for diatoms, silica plays a key role in the estuarine and coastal food web. High concentrations of dissolved silica (DSi) were found in the seepage water of tidal freshwater marshes, which were therefore assumed to contribute to the silica supply to estuarine waters in times of silica limitation. A comprehensive budget calculation for European salt marshes is presented in this study. Earlier, salt marshes were considered to have even higher silica recycling rates than tidal freshwater marshes. Between 2009 and 2011, concentrations, pools and fluxes of silica in two salt marshes at the German Wadden Sea coast were determined (in soil, pore water, aboveground vegetation, freshly deposited sediments and seepage water). Subsequently, a budget was calculated. Special emphasis was placed on the influence of grazing management on silica cycling. Our results show that the two salt marshes were sinks for silica. The average import of biogenic silica (BSi) with freshly deposited sediments (1,334 kmol km^?2 year^?1) largely exceeded the DSi and BSi exports with seepage water (80 kmol km^?2 year^?1). Grazing management can affect silica cycling of salt marshes by influencing hydrology and vegetation structure. Abandoned sites had larger DSi export rates than grazed sites. One third of all BSi imports occurred in only one major flooding, underlining the relevance of rare events in the silica budget of tidal marshes. This aspect has been widely neglected in earlier studies, what might have led to an underestimation of silica import rates to tidal marshes hitherto.     

Nature and reactions of dissolved organic matter in the interstitial waters of marine sediments

Two organic rich sediments, an oxic muddy sand and a silty mud containing sulphate reducing and methane producing metabolic zones, were sampled from Loch Duich, a fjord type estuary in the N.W. coast of Scotland. Dissolved organic carbon (DOC), as measured by dry combustion and UV absorption, remained constant (8.3–15.8 mg C/l) with depth in the oxic pore waters at a concentration at least twice that of the overlying seawater. DOC in the anoxic pore waters increased linearly with depth from 13.6 at the surface to 55.9–70.5 mg C/l at 80cm. Most of the DOC was present in the high molecular weight (HMW) fraction as separated by ultrafiltration; the low molecular weight (LMW) fraction remained constant (10.0 mg C/l) in both oxic and anoxic pore waters. Spectroscopic data showed the ‘humic’ fraction of the HMW dissolved organic matter was mainly fulvic acid, a small proportion (approx 1%) of humic acid, and a third fraction, possibly melanoidins, which increased relative to fulvic acid with depth. These data confirm the pathway of humification (NissenBaum et al, 1971; nissenbaum and Kaplan, 1972) where HMW organic matter accumulates in pore waters as condensation products of LMW organic substances.