Diel variation of selenium and arsenic in a wetland of the Great Salt Lake, Utah

Diel (24-h) changes in Se and As concentrations in a freshwater wetland pond bordering the Great Salt Lake (GSL) were examined. Selenium concentrations (filtered and unfiltered) changed on a diel basis, i.e., were depleted during early morning and enriched during daytime over August 17-18. During the May 24-25, 2006 and September 29-30 diel studies, no significant 24-h trends were observed in Se concentrations compared to August, which showed daily maximums up to 59% greater than the daily minimum. Both filtered and unfiltered As concentrations also varied on a diel cycle, with increased concentrations during early morning and decreased concentrations during daytime. Filtered As concentrations increased 110% during the May 24-25, 2006 diel study. Selenium varied in phase with pH, dissolved O₂ (DO), and water temperature (T_w) whereas As varied opposite to Se, pH, DO and T_w. Changes in pH, DO and T_w showed a direct linear correlation (r = 0.74, 0.75, and 0.55, respectively) to filtered Se. Also pH, DO and T_w were inversely correlated to filtered As concentration (r = −0.88, −0.87, and −0.84, respectively). Equilibrium geochemical speciation and sorption models were used to examine the potential oxidation state changes in Se and As, and sorption and desorption reactions corresponding to the observed 24-h variations in pe and pH. In this wetland it was postulated that diel Se variation was driven by sorption and desorption due to photosynthesis-induced changes in pH and redox conditions. Diel variations of As were hypothesized to be linked to pH-driven sorption and desorption as well as co-precipitation and co-dissolution with mineral phases of Mn.     

Assessment of diel chemical and isotopic techniques to investigate biogeochemical cycles in the upper Klamath River,Oregon, USA

The upper Klamath River experiences a cyanobacterial algal bloom and poor water quality during the summer. Diel chemical and isotopic techniques have been employed in order to investigate the rates of biogeochemical processes.Four diel measurements of field parameters (temperature, pH, dissolved oxygen concentrations, and alkalinity) and stable isotope compositions (dissolved oxygen–δ¹⁸O and dissolved inorganic carbon–δ¹³C) have been performed between June 2007 and August 2008. Significant diel variations of pH, dissolved oxygen (DO) concentration, and DO–δ¹⁸O were observed, due to varying rates of primary productivity vs. respiration vs. gas exchange with air. Diel cycles are generally similar to those previously observed in river systems, although there are also differences compared to previous studies. In large part, these different diel signatures are the result of the low turbulence of the upper Klamath River. Observed changes in the diel signatures vs. sampling date reflect the evolution of the status of the algal bloom over the course of the summer.Results indicate the potential utility of applying diel chemical and stable isotope techniques to investigate the rates of biogeochemical cycles in slow-moving rivers, lakes, and reservoirs, but also illustrate the increased complexity of stable isotope dynamics in these low-turbulence systems compared to well-mixed aquatic systems.     

Diel biogeochemical cycling in a hyperventilating shallow estuarine environment

A diel biogeochemical study was performed to assess the influence that periods of elevated biological activity have on the biogeochemical cycling of macronutrients and redox-sensitive elements in a natural estuarine environment. High-resolution data (15 min sampling) illustrates periodic extreme variations in dissolved oxygen (DO) in the shallow waters of Azevedo Pond, Elkhom Slough, California. During periods of low tidal flushing, DO values can range from highly oxic (>560 μM O₂: >250% saturation) during sunny days to suboxic conditions (<5 μM) at night. Nutrient cycling and redox-sensitive trace element biogeochemistry were evaluated in response to the extreme daily DO fluctuations. A diel sampling study was conducted over a 26-h period, where O₂ concentrations ranged from 346 μM to sustained non-detectable levels in the night hours. In concert with the DO fluctuations, diel phosphate cycling was on the order of 4 μM in response to tidal flushing events and biological assimilation and regeneration. The IO₃ ⁻/I⁻ redox couple quickly responded to suboxic conditions in the water column by a marked increase in I⁻ concentrations and corresponding depletion of IO₃ ⁻. The extreme fluctuations of the p∈ in the water column resulted in diel dissolved Mn²⁺ variations of nearly 5 μM, with observed dissolved Mn removal rates on the order of 1 μM h⁻¹. The elevated biogeochemical cycling of oxygen, nitrogen, phosphorus, iodine, manganese, and iron found in this shallow estuarine environment suggest that tidal restrictions and anthropogenic nutrient enrichments can amplify diel variations and potentially hinder the functional and ecological stability of these systems. These data suggest that accurate chemical monitoring of the health of an estuarine ecosystem must account for the diel variability inherent in these highly productive environments.     

岩溶区河流水化学昼夜变化与生物地球化学过程

河流水化学昼夜动态变化的研究有助于揭示水体中相对快速的生物地球化学过程(河流内过程),同时也有助于判别上游补给区流域过程。已有的研究表明生物过程（光合作用与呼吸作用）、地球化学过程（碳酸盐平衡、碳酸钙沉积）是控制河流pH、SpC、Ca2+和HCO3-含量昼夜变化的主要因素。不同级别、类型及河床微环境均会对水化学昼夜变化产生影响,与气温密切相关的光合作用是产生河水pH值和DO昼夜变化的主控因素。在偏碱性与富含钙离子的岩溶河流,有机体的钙化作用与酸分泌可能对光合作用具有重要作用,从而导致水体中Ca2+和HCO3-出现白天下降-夜间回升的昼夜动态变化,下降幅度达20%~30%。水生植物通过光合作用产生DIC(主要为HCO3-)的原位沉降,是真正意义上的净碳汇。昼夜生物地球化学循环及效应研究有助于全面认识岩溶区碳循环特征及岩溶含水层源汇关系,尤其是岩溶碳汇稳定性与净碳汇估算;同时对长时间尺度河流监测计划的制定具有重要意义。      

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

Discerning vegetation and environmental correlates with subtidal marsh fish assemblage dynamics during<Emphasis Type="Italic">Phragmites</Emphasis> eradication efforts: Interannual trend measures

We examined the 5-yr (1996–2000) response of subtidal marsh creek fishes (2,793 trawls, 47 species, 30,719 fish) to a large marsh restoration project in the upper Delaware Bay, and found that the salinity gradient covaried along with marsh surface vegetation type among two treated and one untreated reference sites, confounding direct comparison of fish utilization. Examination of environmental correlates with monthly yearly trends highlighted differences between potential mechanism driving assemblage dynamics either intrinsic or extrinsic to the marshes. Within-site and among-site differences in fish assemblage, as described by principal components analysis, correlated poorly with marsh vegetation on both seasonal and interannual scales and appeared to driven by larval supply. Assemblage dynamics could be expalined in part by the occurrence of juveniles of transient marine fishes along a salinity gradient (0–15.2%) range in monthly site mean), but were largely determined by fluctuations in the distribution of two transient species: young-of-the-year bay anchovyAnchoa mitchilli and Atlantic croakerMicropogonias undulatus. A minor mode in variance, driven by locally spawned species, was moderately correlated with environmental parameters. Analysis of marshes on an individual basis did not discern additional important gradients. Our findings are in contrast to those in systems dominated by resident species, probably because transient fishes, which often dominante the system, are more plastic to the nature of ecological services or are affected as much by environment outside of the marsh as by that in the marsh.     

Is Ocean Acidification an Open-Ocean Syndrome? Understanding Anthropogenic Impacts on Seawater pH

Ocean acidification due to anthropogenic CO₂ emissions is a dominant driver of long-term changes in pH in the open ocean, raising concern for the future of calcifying organisms, many of which are present in coastal habitats. However, changes in pH in coastal ecosystems result from a multitude of drivers, including impacts from watershed processes, nutrient inputs, and changes in ecosystem structure and metabolism. Interaction between ocean acidification due to anthropogenic CO₂ emissions and the dynamic regional to local drivers of coastal ecosystems have resulted in complex regulation of pH in coastal waters. Changes in the watershed can, for example, lead to changes in alkalinity and CO₂ fluxes that, together with metabolic processes and oceanic dynamics, yield high-magnitude decadal changes of up to 0.5 units in coastal pH. Metabolism results in strong diel to seasonal fluctuations in pH, with characteristic ranges of 0.3 pH units, with metabolically intense habitats exceeding this range on a daily basis. The intense variability and multiple, complex controls on pH implies that the concept of ocean acidification due to anthropogenic CO₂ emissions cannot be transposed to coastal ecosystems directly. Furthermore, in coastal ecosystems, the detection of trends towards acidification is not trivial and the attribution of these changes to anthropogenic CO₂ emissions is even more problematic. Coastal ecosystems may show acidification or basification, depending on the balance between the invasion of coastal waters by anthropogenic CO₂, watershed export of alkalinity, organic matter and CO₂, and changes in the balance between primary production, respiration and calcification rates in response to changes in nutrient inputs and losses of ecosystem components. Hence, we contend that ocean acidification from anthropogenic CO₂ is largely an open-ocean syndrome and that a concept of anthropogenic impacts on marine pH, which is applicable across the entire ocean, from coastal to open-ocean environments, provides a superior framework to consider the multiple components of the anthropogenic perturbation of marine pH trajectories. The concept of anthropogenic impacts on seawater pH acknowledges that a regional focus is necessary to predict future trajectories in the pH of coastal waters and points at opportunities to manage these trajectories locally to conserve coastal organisms vulnerable to ocean acidification.     

Hydrographic characterization of two tidal creeks with implications for watershed land use,flushing times,and benthic production

Many coastal ecosystems are undergoing anthropogenic stress from large increases in population and urbanization. In many regions changes in freshwater and material inputs to the coastal zone are altering the biogeochemical and biological capacities of ecosystems. Despite increased watershed inputs, large tidal volumes and flushing indicative of macrotidal estuaries can modulate the fate of introduced materials masking some of the symptoms of eutrophication. The Land Use Coastal Ecosystem Study (LU-CES) examined linkages between land use and environmental properties of Malind and Okatee Creeks in South Carolina from 2001 to 2004. The objectives of this particular study were to assess the hydrography of the two macrotidal creek ecosystems, explore differences in dissolved oxygen (DO), and develop a better understanding of the variations in primary and benthic secondary production in southeastern creek ecosystems. Depth, pH, salinity, and DO were reduced and more variable in Malind Creek than in Okatee Creek, although both creeks had strong semidiurnal frequencies in salinity time signatures. While time series analyses of DO saturation in Malind Creek revealed a dominant semidiurnal pattern, Okatee Creek had a distinctly diel DO pattern. The strongly semidiurnal fluctuations in DO and reduced flushing time indicated that biological processes were not fast enough to influence DO in Malind Creek. The Okatee Creek system had a much greater storage volume, a wider marsh, and a dominant 25-h DO frequency. These attributes contributed to an estimated 8–10 times more phytoplankton-based carbon in Okatee Creek and twice the annual benthic production. As expected from their proximity to the upland, low surface area, and high organic content, both ecosystems were net heterotrophic. This fundamental understanding of tidal creek hydrography is being used to help define linkages among differential watershed land uses, flushing characteristics, and levels of biological production in coastal ecosystems of the southeastern United States.     

Diel vertical migration of zooplankton in contrasting habitats of the Chesapeake Bay

Two different habitats in the Chesapeake Bay were tested for the occurrence of diel vertical migration (DVM) by members of the zooplankton community. During July of 1997 diel samples were collected from Jones Creek, a small, protected, 3-m deep tidal gut, and a station in Hampton Roads, a 20-m deep, expansive section of the bay. Temperature, salinity, light penetration, water clarity, dissolved oxygen, total particulate nitrogen and carbon, chlorophyll concentration, and algal density were also determined for depth increments at these stations, ca. midday and midnight. Significant differences in zooplankton depth distribution occurred over the day at both stations. The calanoid copepod,Acartia tonsa, dominated the zooplankton community and the larger stages were strong migrators. Mysid shrimp, the largest sized crustaceans, displayed significant DVM at both stations. Although diel differences were also detected in chlorophylla concentrations, with 25% reduction at night in Jones Creek and 18% in Hampton Roads, counts of algal cells revealed no differences between night and day numbers. The nightly losses of chlorophyll were not driven by mesozooplankton grazers. Using grazing rates from the literature, we estimated that mesozooplankton harvested less than 5% of the standing crop of phytoplankton each day in both locations. Food quantity and quality (as determined by chlorophyll concentrations, cell counts, and C:N ratio) were uniform in the Jones Creek water column, but higher near the surface in Hampton Roads. While it was clearly advantageous for zooplankton to migrate to surface waters at night for feeding in Hampton Roads, it is paradoxical for DVM to persist in Jones Creek when ample food was found in deeper water.     

A chlorophyll time series for Narragansett Bay: Assessment of the potential effect of tidal phase on measurement

An 18-yr chlorophyll time series for Narragansett Bay based on weekly samples collected without regard to tidal phase revealed a long-term decrease in mean annual levels. The potential influence of neglecting tidal phase in the sampling strategy on measured chlorophyll and its apparent long-term decrease is evaluated. A two year data set (1995–1996) is used as a proxy for the 1973–1990 time series together with an observed relationship between continuous measurements of in situ chlorophyll fluorescence and accompanying tidal phase. The deviations in chlorophyll from long-term means relative to deviations from mean low water at the time of sample collection are also analyzed, as is the potential influence of tidally-induced advective increases or dilution on measured chlorophyll levels. The analyses, which compare the magnitude and trends in tidally adjusted and directly measured chlorophyll, indicate that semi-diurnal intratidal variations in chlorophyll had little apparent effect on the long-term and seasonal patterns and trends deduced from the chlorophyll measurements. Neither tidal advection of the chlorophyll gradient, nor bloom magnitude appear to compromise application of the model. The 18-yr decline in annual mean chlorophyll observed between 1973–1990 in narragansett Bay is considered to be a bonafide portrayal of actual events, and not an artifact of failure to consider tidal phase in the weekly sampling strategy. The results also suggest that intratidal variability in chlorophyll does not seriously confound its meaningful measurement and usefulness as a representative index of phytoplankton abundance at the permanent monitoring station established for Narragansett Bay. Nonetheless, there is need to refine and to incorporate temporal sampling strategies more closely attuned to the tempo of growth, grazing, and nutrient recycling which accompany estuarine phytoplankton dynamics.     

Distribution of glycerol dialkyl glycerol tetraethers in surface sediments of Lake Qinghai and surrounding soil

Glycerol dialkyl glycerol tetraethers (GDGTs) are increasingly used as proxies for paleoclimate studies of marine and lacustrine environments. While GDGT-based proxies have been applied to a number of lake environments globally, little is known about the distribution of GDGTs on the Qinghai-Tibet Plateau. We have investigated the isoprenoid GDGTs (iGDGTs) and branched GDGTs (bGDGTs) in Lake Qinghai sediments and the surrounding surface soil in order to examine their potential use as paleoclimate proxies on the Qinghai-Tibet Plateau. The results show that (i) the values of the iGDGT/bGDGT ratio for surrounding soil were at the higher end among globally distributed soils and consequently BIT values (avg. 0.71) at the lower end, (ii) the TEX₈₆ values decreased while the MBT and CBT values increased along an onshore soil–nearshore sediment–offshore sediment transect, (iii) the TEX₈₆ values for the offshore sediments were almost identical and their inferred temperatures were close to mean summer surface water temperature and (iv) the bGDGT-inferred mean annual air temperature (MAAT) and pH for soil were consistent with measured MAAT and pH. However, the CBT-inferred pH for offshore sediments seemed inconsistent with the pH of lake water or sediment. Our results suggest that (i) the higher pH may be an important factor leading to the higher iGDGT/bGDGT values (and lower BIT values) in surrounding surface soil, (ii) both iGDGTs and bGDGTs may originate from terrestrial input and in situ production for this saline lake, especially for nearshore sediments. However, for offshore sediments, terrestrial iGDGT input seems minor, and TEX₈₆ may be useful for paleoclimate studies of Lake Qinghai.     

Fish assemblage stability over fifty years in the Lake Pontchartrain estuary; Comparisons among habitats using canonical correspondence analysis

We assessed fish assemblage stability over the last half century in Lake Pontchartrain, an environmentally degraded oligohaline estuary in southeastern Louisiana. Because assemblage instability over time has been consistently associated with severe habitat degradation, we attempted to determine whether fish assemblages in demersal, nearshore, and pelagic habitats exhibited change that was unrelated to natural fluctuations in environmental variables (e.g., assemblage changes between wet and dry periods). Collection data from three gear types (trawl, beach seine, and gill nets) and monthly environmental data (salinity, temperature, and Secchi depth) were compared for four collecting periods: 1954 (dry period), 1978 (wet period), 1996–1998 (wet period), and 1998–2000 (dry period). Canonical correspondence analysis (CCA) revealed that although the three environmental variables were significantly associated with the distribution and abundance patterns of fish assemblages in all habitats (with the exception of Secchi depth for pelagic samples), most fish assemblage change occurred among sampling periods (i.e., along a temporal gradient unrelated to changing environmental variables). Assemblage instability was the most pronounced for fishes collected by trawls from demersal habitats. A marked lack of cyclicity in the trawl data CCA diagram indicated a shift away from a baseline demersal assemblage of 50 yr ago. Centroid positions for the five most collected species indicated that three benthic fishes, Atlantic croaker (Micropogonias undulatus), spot (Leiostomus xanthurus), and hardhead catfish (Arius felis), were more dominant in past demersal assemblages (1954 and 1978). A different situation was shown for planktivorous species collected by trawls with bay anchovy (Anchoa mitchilli) becoming more dominant in recent assemblage and Gulf menhaden (Brevoortia patromus) remaining equally represented in assemblages over time. Changes in fish assemblages from nearshore (beach seine) and pelagic (gill net) habitats were more closely related to environmental fluctuations, though the CCA for beach seine data also indicated a decrease in the dominance ofM. undulatus and an increase in the proportion ofA. mitchilli over time. The reduced assemblage role of benthic fishes and the marked assemblage change indicated by trawl data suggest that over the last half century demersal habitats in Lake Pontchartrain have been impacted more by multiple anthropogenic stressors than nearshore or pelagic habitats.     

水生植物对岩溶区河水地球化学昼夜变化的影响——以漓江为例

为研究河流非岩溶区断面和岩溶区断面生物地球化学昼夜变化过程、特征及影响因素,探讨水生生物对岩溶区河水碳汇作用的影响,于2016年10月30日-2016年11月1日,在广西桂林漓江干流非岩溶区的峡背和岩溶区的省里设置两个监测点同时开展了为期48小时的高分辨率在线监测和高频率取样工作,研究其水文参数(电导率(EC)、水温(T)、pH以及Ca2+、HCO-3、NO-3等离子和溶解无机碳同位素(δ13CDIC)等水化学参数的昼夜变化规律,并分析其影响因素。发现:（1）峡背和省里两断面水化学类型为HCO3－Ca型,但水文地球化学昼夜变化过程不同:省里断面的物理化学参数昼夜变化显著,T、pH、DO、SIC白天上升夜间下降,Ca2+、HCO-3的质量浓度和EC、p (CO2)白天降低、夜晚上升;而峡背断面理化指标昼夜变幅小,这与峡背断面处于岩溶区与非岩溶区交界处,非岩溶河流汇入、生物量较小等环境特征有关。（2）省里断面营养元素(NO-3、SO42-、Cl-、Na+)昼夜变化过程主要受水生植物同化作用控制,呈现白天降低、夜间升高的变化规律。（3）峡背断面和省里断面TOC 与DOC白天上升、夜间下降,最高日变化幅度可达79%和61%,利用端元混合模型计算得出省里断面和峡背断面内源有机碳占总有机碳的比例分别为91.99%和88.39%,省里断面和峡背断面水生植物光合作用利用HCO-3作为无机碳源的比例为67.42%～99.75%和57.76%～69.78%,平均值分别为79.54%和63.13%。（4）省里断面溶解无机碳(DIC)变化范围为67.1～115.9 mg·L-1,平均值为96.5 mg·L-1,呈现白天下降夜间上升的变化。δ13CDIC变化范围-7.8‰～-9.9‰,平均值为-8.9‰,表现为白天偏重、晚上偏轻的动态变化,两者呈显著的负相关关系(相关系数为-0.79)。研究表明省里断面水生植物光合作用和呼吸作用以及钙沉降是控制DIC昼夜变化的主导因素。通过估算监测期间省里断面光合作用DIC转化速率平均值为1.2×10-5 mmol·L-1·S-1,Ca2+离子的沉积速率平均值为0.18×10-5mmol·L-1·S-1。因此,岩溶区河段水生生物光合作用及其固碳能力较非岩溶区河段明显增强。      

Behavior of stable isotopes of dissolved oxygen,dissolved inorganic carbon and nitrate in groundwater at a former wood treatment facility containing hydrocarbon contamination

The speciation and mobility of a variety of chemical species in groundwater are strongly influenced by redox and pH conditions. Dissolved O₂ (DO) and dissolved inorganic C (DIC) concentrations are significant controls of these conditions, respectively. It is not always clear what the major processes are that influence changes in the concentration of DO and DIC across a groundwater flowpath. The combined use of the stable isotope compositions of DO (δ¹⁸O–DO) and DIC (δ¹³C–DIC) has the potential to help investigators discriminate between sources and sinks of DO and DIC in groundwater systems.     

Comparison of habitat use by estuarine fish assemblages in the Acadian and Virginian zoogeographic provinces

Comparison of the relative abundance of fish species from different life-history groups and their temporal patterns of estuarine habitat use from two estuaries north and south of Cape Cod indicates that the Cape acts as a zoogeographic boundary. Between April 1988 and December 1989, monthly seine and trawl samples were collected from nearshore, shallow-water marsh, and beach and deeper open-water habitats in Wells Harbor, Maine, and Waquoit Bay, Massachusetts. Forty-eight species and 80,341 individuals were collected from Waquoit Bay compared to 24 species and 22,561 individuals from Wells Harbor. Waquoit Bay had proportionally fewer resident species and more marine, nursery, and occasional species than Wells Harbor. Annual density and biomass values were greater across all habitats in Waquoit Bay, with the summer values from the marsh habitat an order of magnitude higher than comparable summer data from the Wells habitats. We suggest that marsh and beach habitats provide a nursery area for young-of-the-year fishes, while deeper, open-water habitats serve as a corridor for fishes moving to nearshore habitats or serve as a refuge during low tide.     

Interannual and long-term variation in the nearshore fish community of the mesohaline Hudson River estuary

The detection of long-term shifts in species composition and spatial structuring of aquatic communities may be obscured by high levels of interannual variation. Estuarine fish communities are likely to exhibit high levels of variation owing to the influence of riverine forcing and the importance of anadromous and transient species, whose abundances may not be locally controlled. We describe patterns of interannual variation and long-term shifts in the nearshore fish community of the mesohaline Hudson River estuary based on 21 yr of beach seine sampling conducted annually between late August and mid November. Of the 60 species encountered, the most abundant were Atlantic silversides (Menidia menidia), striped bass (Morone saxatilis), white perch (Morone americana), American shad (Alosa sapidissima), and blueback herring (Alosa aestivalis). Relationships between annual community composition and seasonal flow and temperature regimes were examined with canonical correspondence analysis. Annual variation was most closely correlated with river flows in the 3-mo period preceding fish sampling, indicating a persistent effect of environmental conditions on community structure. Despite significant interannual variation in composition, longer-term trends in community structure were observed. These included declines in catch rates of freshwater and estuarine species and a dramatic increase in the catch of Atlantic silversides, an annual marine species. Associated with these changes were declines in community diversity and increased compositional variation. These results indicate that analyses of temporal changes in community structure need to account for the multiple time scales under which forcing factors and community composition vary.     

Short-term changes in water chemistry in the Baccu Locci stream (Sardinia,Italy) affected by past mining

Short-term changes in water chemistry, and especially in dissolved trace element concentrations, associated with diel cycles during base-flow conditions at a specific sampling station in the Baccu Locci stream draining the homonymous old mine area in Sardinia (Italy) were investigated. Diel fluctuations in pH and alkalinity were correlated with the temperature-dependent CO₂ solubility and the biologically-induced CO₂ production, both of which were higher during the night. Adsorption/desorption to/from streambed material, in particular ferrihydrite, is believed to be the main in-stream mechanism causing the observed diel variations in dissolved concentrations of As and Zn. Arsenic was mainly affected by the dual action of temperature and competing carbonate ions, whereas pH seemed less important. Temperature acted in accordance with the exothermic feature of anion sorption onto hydrous metal oxide surfaces; aqueous carbonate species exerted their competitive effect in relation to alkalinity variation. Zinc was primarily affected by temperature, in accordance with the endothermic feature of metal cation sorption onto hydrous metal oxide surfaces, and secondly by pH. Co-precipitation of As and Zn with calcite is another possible mechanism, which requires further investigation involving examination of inorganic and biological materials coating the streambed. All these processes potentially controlling the diel cycles of trace elements should be carefully considered to assess the effectiveness of remediation actions currently in progress at Baccu Locci. A normalization method for data from asynchronous sampling has been developed and proposed in order to eliminate or at least attenuate the effect of sampling time and provide an additional tool to identify the processes/mechanisms involved in trace element concentration fluctuations observed along a contaminated stream during base-flow conditions.     

Intraseasonal oscillations and interannual variability of surface winds over the Indian monsoon region

The role of intraseasonal oscillations (ISOs) in modulating synoptic and interannual variations of surface winds over the Indian monsoon region is studied using daily averaged National Centers for Environmental Prediction/National Centre for Atmospheric Research (NCEP/NCAR) reanalyses for the period 1987–1996. Two dominant ISOs are found in all years, with a period between 30–60 days and 10–20 days respectively. Although the ISOs themselves explain only about 10–25% of the daily variance, the spatial structure of variance of the ISOs is found to be nearly identical to that of high frequency activity (synoptic disturbances), indicating a significant control by the ISOs in determining the synoptic variations. Zonal and meridional propagation characteristics of the two modes and their interannual variability are studied in detail. The synoptic structure of the 30–60 day mode is similar in all years and is shown to be intimately related to the strong (‘active’) or weak (‘break’) phases of the Indian summer monsoon circulation. The peak (trough) phase of the mode in the north Bay of Bengal corresponds to the ‘active’ (‘break’) phase of monsoon strengthening (weakening) the entire large scale monsoon circulation. The ISOs modulate synoptic activity through the intensification or weakening of the large scale monsoon flow (monsoon trough). The peak wind anomalies associated with these ISOs could be as large as 30% of the seasonal mean winds in many regions. The vorticity pattern associated with the 30–60 day mode has a bi-modal meridional structure similar to the one associated with the seasonal mean winds but with a smaller meridional scale. The spatial structure of the 30–60 day mode is consistent with fluctuations of the tropical convergence zone (TCZ) between one continental and an equatorial Indian Ocean position. The 10–20 day mode has maximum amplitude in the north Bay of Bengal, where it is comparable to that of the 30–60 day mode. Elsewhere in the Indian Ocean, this mode is almost always weaker than the 30–60 day mode. In the Bay of Bengal region, the wind curl anomalies associated with the peak phases of the ISOs could be as large as 50% of the seasonal mean wind curl. Hence, ISOs in this region could drive significant ISOs in the ocean and might influence the seasonal mean currents in the Bay. On the interannual time scale, the NCEP/NCAR reanalysed wind stress is compared with the Florida State University monthly mean stress. The seasonal mean stress as well as interannual standard deviation of monthly stress from the two analyses agree well, indicating absence of any serious systematic bias in the NCEP/NCAR reanalysed winds. It is also found that the composite structure of the 30–60 day mode is strikingly similar to the dominant mode of interannual variability of the seasonal mean winds indicating a strong link between the ISOs and the seasonal mean. The ISO influences the seasonal mean and its interannual variability either through increased/decreased residence time of the TCZ in the continental position or through occurrence of stronger/weaker active/break spells. Thus, the ISOs seem to modulate all variability in this region from synoptic to interannual scales.     

Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe²⁺ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters.     

Diel variation of arsenic,molybdenum and antimony in a stream draining natural As geochemical anomaly

The Mokrsko Stream in the central Czech Republic is an oxic and slightly alkaline stream that drains a natural As geochemical anomaly. Although long-term monitoring has characterized the general seasonal trends in trace element concentrations (i.e., As, Mo, Cu, Zn) in this stream, little is known about solubility controls and sorption processes that influence diel cycles in trace element concentrations. Trace elements (including As species, Cu, Mn, Mo, Pb and Sb) and other parameters were monitored over two 24-h periods in unfiltered and filtered (0.1 μm) samples collected in August 2010 and June 2011. Copper and Pb were predominantly (>92% of the mass) associated with the particulate fraction (>0.1 μm). Arsenic, Mo and Sb were predominantly (>88% of the mass) in the “dissolved” (<0.1 μm) form. Particulate-associated elements displayed up to a factor of 13 differences between minimum and maximum concentrations, most likely due to increased streamflow related to rainfall events. Dissolved concentrations of the trace metal cations (Cu, Fe, Mn and Pb) were consistently low and displayed no diel trends. Dissolved As(V), Mo and Sb varied on a diel cycle, with increased concentrations (up to 36%) during the late afternoon and decreased concentrations during the nighttime. Diel trends in trace anionic elements are explained by temperature-dependent sorption, as the diel changes in pH during base flow were very small (0.07 std. units). Very low concentrations of As(III), which have been shown to vary in a diel cycle, were attributed to enhanced hydraulic exchange with As(III)-rich hyporheic water during rainfall events.