A multi-method approach for the identification and quantification of water balance components of two lentic small water bodies

The protection of the globally widespread lentic small water bodies (LSWB) must be based on detailed knowledge about their hydrological connectivity and water balance. The study aimed to identify and quantify water balance components as well as surface-groundwater interaction of two LSWB in a characteristic lowland region with a combination of different methods. This includes the collection of hydrological data and the use of bromide and water stable isotopes (δ²H and δ¹⁸O) as tracers. With their help, mixing models were established, and daily water balances were assessed. The results show a strong bidirectional interaction of both LSWB systems with shallow groundwater. Bromide and stable isotope tracers allowed for the identification of the most relevant in- and outflow sources and pathways. Thereby, isotope data revealed isotopic enrichment typical for open-water bodies and only minor precipitation inputs mainly relevant at the end of the dry season. Water balance calculations suggested accentuated seasonal dynamics that were strongly influenced by shallow groundwater, which represented large inputs into both LSWB. By that, different phases could be identified, with high inflow rates in winter and spring and decreasing fluxes in summer. In one LSWB, a drainage system was found to have a major impact next to the shallow groundwater interaction. The findings of this research provide detailed insights into the influence and importance of shallow groundwater for LSWB in lowland regions. This impacts the diffuse input of agricultural pollutants into these ecologically important landscape features.     

Stable isotopes of water reveal differences in plant – soil water relationships across northern environments

We compared stable isotopes of water in plant stem (xylem) water and soil collected over a complete growing season from five well-known long-term study sites in northern/cold regions. These spanned a decreasing temperature gradient from Bruntland Burn (Scotland), Dorset (Canadian Shield), Dry Creek (USA), Krycklan (Sweden), to Wolf Creek (northern Canada). Xylem water was isotopically depleted compared to soil waters, most notably for deuterium. The degree to which potential soil water sources could explain the isotopic composition of xylem water was assessed quantitatively using overlapping polygons to enclose respective data sets when plotted in dual isotope space. At most sites isotopes in xylem water from angiosperms showed a strong overlap with soil water; this was not the case for gymnosperms. In most cases, xylem water composition on a given sampling day could be better explained if soil water composition was considered over longer antecedent periods spanning many months. Xylem water at most sites was usually most dissimilar to soil water in drier summer months, although sites differed in the sequence of change. Open questions remain on why a significant proportion of isotopically depleted water in plant xylem cannot be explained by soil water sources, particularly for gymnosperms. It is recommended that future research focuses on the potential for fractionation to affect water uptake at the soil-root interface, both through effects of exchange between the vapour and liquid phases of soil water and the effects of mycorrhizal interactions. Additionally, in cold regions, evaporation and diffusion of xylem water in winter may be an important process.     

On the Measurement of PANs by Gas Chromatography and Electron Capture Detection

A fast, automated, gas chromatographic system for the airborne measurement of PAN and a series of its homologues is described and its performance is evaluated. Response factors for PAN, PPN, APAN, PiBN, and MPAN have been determined and are discussed with regard to ECD response and to potential losses in the analytical system. Calibration methods used for these tasks are described and compared. The results from this work should help investigators who are employing the widely used GC/ECD method for the measurement of peroxyacyl nitrates to evaluate peaks of PAN homologues that cannot be calibrated for by using the reported response factors.     

The removal rates of234Th and228Th from waters of the New York Bight

The mean residence time (τ) of thorium with respect to non-radioactive removal from water was determined as a function of location in three traverses of the New York Bight using both²³⁴Th/²³⁸U and²²⁸Th/²²⁸Ra. τ correlates well with salinity increasing from about ten days near shore to 70 days at the shelf break. It shows a much weaker correlation with suspended matter concentrations both because suspended matter varies in its scavenging efficiency and because salinity is a longer-term integrator of scavenging potential.τ's computed from²²⁸Th/²²⁸Ra were often higher than those computed from²³⁴Th/²³⁸U either because of the detrital matter present as reflected in the²³²Th concentrations or because the water parcels had recently arrived from environments of lower scavenging efficiency.Anomalous isotopic concentrations found in three adjacent samples can best be explained as the result of an episodic release of²²⁸Ra from bottom sediments at a rate 200 times the normal one.     

How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II), mn(II), and S(?II) in undisturbed soils and sediments using voltammetry

Background

Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach??the pilot ion method??has not been documented in detail.

Results

A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II) and Mn(II), subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II) to Fe(II) varied by no more than 11% from one Hg/Au electrode to another and Fe(II) concentrations predicted by the Mn(II) pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15???M Fe(II) (46% different on average). The ratio of calibration slopes of Mn(II) to S(?II) varied by almost 20% from one Hg/Au electrode to another, and S(?II) predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II) and S(?II) concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At medium-to-high concentration for the ocean, naturally derived dissolved organic carbon did not significantly affect the baseline-corrected electrode response of Mn(II) and Fe(II), but did significantly affect the response of S(?II).

Conclusions

Despite their intrinsic variability, Hg/Au electrodes fabricated by hand can be used to quantify O₂, S(?II), Fe(II), and Mn(II) without calibrating every electrode for every constituent of interest. The pilot ion method can achieve accuracies to within 20% or less, provided that the underlying principle??the independence of slope ratios??is demonstrated for all voltammetric techniques used, and effects of the physicochemical properties of the system on voltammetric signals are addressed through baseline subtraction.     

Changes in fine sediment size distributions due to interactions with streambed sediments

In the classical view of fine sediment transport and deposition in streams, particles are expected to be removed from flowing water simply by direct sedimentation onto the streambed. However, recent research has demonstrated that fine sediments can propagate into pore spaces in the streambed due to hyporheic exchange and be removed by a combination of physical and chemical processes. This behaviour can significantly alter fine sediment size distributions during in-stream sediment transport because the physical transport of fine particles and their attachment to bed sediment grains are both a function of the particle size. Herein, we present model simulations for deposition of suspended sediments with a bimodal size distribution. We also applied this approach to analyse the results of laboratory flume observations of suspended sediment deposition. Results from model simulations and flume experiments clearly show that the rate of particle deposition increases with increasing particle size. Thus, the larger particles are preferentially removed from mixtures and there is a fining of the mixed suspensions over time. Both particle deposition mechanisms, i.e. particle sedimentation and filtration, contribute to the fining of the mixed fine particle suspensions over time, and their effects are clearly demonstrated using the fundamental process-based model. These results clearly demonstrate the effects of stream-subsurface exchange on the temporal evolution of the suspended fine sediment size distribution in downstream transport.     

The effect of distribution of iron-oxyhydroxide grain coatings on the transport of bacterial cells in porous media

 Among the demonstrated processes influencing the transport of bacteria through aquifers, the deposition of cells on mineral surfaces is one of the most important. For example, understanding the transport of introduced bacteria through aquifers is essential to designing some in situ bioremediation schemes. The impact of the presence and distribution of Fe(III)-oxyhydroxide-coated sand grains on bacterial transport through porous media was evaluated in column experiments in which bacteria (short rods; 1.2 μm length) were eluted through columns of quartz sand (0.5–0.6 mm in diameter) for several conditions of chemical heterogeneity of mineral substrate. Fe(III)-oxyhydroxide-coated sand was present as 10% of the mass, and it was arranged in three treatments: (1) homogeneously distributed, and present as a discrete layer (2) at the top and (3) at the bottom of 14-cm-long sand columns. A pulse input of 10⁸ cells ml^–1 was introduced in an artificial groundwater solution flowing at 14 cm h^–1 through the column, and eluted cells were counted. Peak breakthrough occurred at 1.0 pore volume. A large proportion of cells were retained; 14.7–15.8% of the cells were recovered after three pore volumes of solution had eluted through clean quartz sand, and only 2.1–4.0% were recovered from the Fe(III)-oxyhydroxide-coated sand mixtures. The three physical arrangements of the chemical heterogeneity resulted in essentially the same breakthrough of cells, indicating that the spatial distribution of iron coating does not affect the transport of bacteria. The results of the column transport experiments, which mimic hydrogeological conditions encountered in field problems, are consistent with our mechanistic understanding of bacterial sorption. Received: 10 April 1996 · Accepted: 17 February 1997     

Climate influences on water and sediment properties of Genovesa Crater Lake,Galápagos

Genovesa Crater Lake is a remote, hypersaline lake in the northern Galápagos archipelago that contains a finely laminated sediment record. This sediment record has the potential to provide a high-resolution history of past climate variability in the eastern tropical Pacific. Here we present modern climate, lake, and sediment observations from 2009 to 2012 to explore how local climate variability influences Genovesa Crater Lake and its sediments. Surface lake temperature is strongly linked to air temperature and is highly seasonal. Temperature stratification is strongest during the warm season, whereas temperature becomes more uniform through the water column in the cool season. Deeper and earlier mixing occurred during the 2010 La Niña, which subsequently delayed 2011 cool season mixing and maximum warm season surface temperatures in 2011 and 2012. Lake salinity changes are influenced by precipitation, evaporation and persistent seawater influx. The largest declines in subsurface salinity follow months after the rainy season, when temperatures cool and fresher surface water from the previous warm/wet season mixes into the subsurface. Between 2009 and 2012, more calcium carbonate precipitated during a period of higher salinity. The period of highest calcium carbonate abundance measured in sediment records that span the late nineteenth to twentieth century coincides with the failure of two consecutive rainy seasons in 1988 and 1989 as well as the coldest monthly sea surface temperature measured at Puerto Ayora in 1989. More calcium carbonate-rich laminae from AD 1550 ± 70 to 1675 ± 90 may indicate a greater frequency of prolonged droughts or cooler temperatures, although enhanced productivity may also modulate carbonate precipitation. More Ca-rich laminae in Genovesa coincide with dry conditions inferred from other Galápagos sediment proxies, as well as prolonged dry and cool conditions inferred from reconstructions of the Southern Oscillation Index and NINO3 sea surface temperatures.     

Water policy,trust and governance in the Murray-Darling Basin

Concerns for river health in the Murray-Darling Basin (MDB) area and shifting priorities for water use have led to a significant process of water reform over the last decade. The MDB area, also known as the food bowl of Australia, produces much of the country's food and is home to a significant portion of the population. A long-term drought, historical over-allocation of water for irrigation and climate variability have led to mounting concerns about the long-term viability of the rivers. While the reform process has resulted in the Commonwealth government taking control of the rivers from the States, it has also been influenced by changes in governments and consequent shifts in water allocation priorities from a privileging of agriculture to a broader approach encompassing economic, environmental and social concerns. This had led to uncertainty for the people and communities in the Basin and some confusion between the various layers of governance structures. This paper presents the results of exploratory research conducted with key, high-level stakeholders involved in water reform to examine their perceptions of the evolving water policy process. Despite agreement amongst stakeholders that returning water to the environment to ensure river health is critical, our research reveals significant tensions between stakeholders concerning the evolving process, particularly centred on the potential social outcomes and fairness and equity. This suggests the need for more integrated and transparent governance structures, attention to levels of trust between partners and a common vision that incorporates environmental, economic and social goals.