Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for delta(18)O, delta(2)H, non-volatile dissolved organic carbon (NVDOC), SO(4)(2-), NO(3)(-) and Cl(-). Monthly recharge amounts were quantified using the offset of the delta(18)O or delta(2)H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO(4)(2-) in the top 1 to 2 m of the saturated zone was associated with recharge; SO(4)(2-) averaged 2.2 mM, with maximum concentrations of 15 mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6 mM. Temporal monitoring of delta(2)H and SO(4)(2-) showed that vertical transport of recharge carried SO(4)(2-) to depths up to 1.75 m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of delta(34)S in SO(4)(2-) indicated both SO(4)(2-) reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO(4)(2-) reduction rates, calculated using the natural Cl(-) gradient as a conservative tracer, ranged from 7.5x10(-3) to 0.61 mM.d(-1) (over various depth intervals from 0.45 to 1.75 m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO(4)(2-) reduction rates were higher at the contaminated site. Although estimated SO(4)(2-) reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO(4)(2-) reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2 m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO(4)(2-) reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers.     

Managing Dive Tourism for the Sustainable Use of Coral Reefs: Validating Diver Perceptions of Attractive Site Features

It has been argued that strategies to manage natural areas important for tourism and recreation should integrate an understanding of tourist preferences for specific natural features. However, the accuracy of tourist recalled perceptions of environmental attributes, which are usually derived from post hoc surveys and used to establish management priorities, is currently unmeasured. We tested the validity of the relationship between tourist-stated preferences and actual condition of coral reefs around the Caribbean island of Bonaire. Using standardized questionnaires, we asked 200 divers to select their most and least favorite dive sites and the attributes that contributed to that selection. We also carried out ecological surveys at 76 of the 81 dives sites around the island to assess the actual conditions of the attributes indicated as important for site selection. Fish- and coral-related attributes were key features affecting dive enjoyment. In general, divers appeared to be able to perceive differences between sites in the true condition of biological attributes such as fish species richness, total number of fish schools, live coral cover, coral species richness, and reef structural complexity, although men and women divers differed in their ability to perceive/recall some of the attributes. Perceived differences in environmental attributes, such as surface conditions, underwater current, and the likelihood of encountering rare fish and sea turtles, were not empirically validated. The fact that divers perceive correctly differences in the condition of some of the key biological attributes that affect dive enjoyment reinforces the need to maintain overall reef condition at satisfactory levels. However, variation in accuracy of perceptions owing to demographic factors and attribute type suggests the need for caution when using public perceptions to develop environmental management strategies, particularly for coral reefs.     

Determination of dominant biogeochemical processes in a contaminated aquifer-wetland system using multivariate statistical analysis

Determining the processes governing aqueous biogeochemistry in a wetland hydrologically linked to an underlying contaminated aquifer is challenging due to the complex exchange between the systems and their distinct responses to changes in precipitation, recharge, and biological activities. To evaluate temporal and spatial processes in the wetland-aquifer system, water samples were collected using cm-scale multi-chambered passive diffusion samplers (peepers) to span the wetland-aquifer interface over a period of 3 yr. Samples were analyzed for major cations and anions, methane, and a suite of organic acids resulting in a large dataset of over 8000 points, which was evaluated using multivariate statistics. Principal component analysis (PCA) was chosen with the purpose of exploring the sources of variation in the dataset to expose related variables and provide insight into the biogeochemical processes that control the water chemistry of the system. Factor scores computed from PCA were mapped by date and depth. Patterns observed suggest that (i) fermentation is the process controlling the greatest variability in the dataset and it peaks in May; (ii) iron and sulfate reduction were the dominant terminal electron-accepting processes in the system and were associated with fermentation but had more complex seasonal variability than fermentation; (iii) methanogenesis was also important and associated with bacterial utilization of minerals as a source of electron acceptors (e.g., barite BaSO(4)); and (iv) seasonal hydrological patterns (wet and dry periods) control the availability of electron acceptors through the reoxidation of reduced iron-sulfur species enhancing iron and sulfate reduction.     

A phycocyanin probe as a tool for monitoring cyanobacteria in freshwater bodies

In many countries, the presence of cyanobacteria in freshwater bodies used for both drinking water and recreational purposes is under increasing public health attention. Water managers are considering how to implement monitoring that leads to a minimization of the risks incurred by the users of potentially contaminated sites. To address this question, this study involved assessing the performance of a submersible probe for measuring phycocyanin-specific fluorescence as a function of cyanobacterial biomass, with the aim of applying it as a tool for surveillance management. Its advantages and limits compared to more traditional analyses are discussed. The monitoring of cyanobacteria in the water bodies of western France was carried out using a minifluorimeter specific to the fluorescence of phycocyanin, a pigment specific to cyanobacteria. The results are compared with the analyses recommended by the World Health Organisation (chlorophyll a and cell counting). This study based on nearly 800 samples shows a significant correlation between the phycocyanin content and the cyanobacterial biomass, expressed as the number of cells per mL (R2 = 0.73). This submersible probe is simple and rapid to use, making it possible to take into account horizontal and vertical heterogeneities in the proliferation growth. In this way, we are able to detect at an early stage the conditions that could potentially lead to a risk, in order to start sampling. Due to its sensitivity, this tool proves suitable for monitoring aimed at reducing the risks incurred by the users of contaminated sites and launching preventative actions. The use of the phycocyanin probe provides an effective tool to complement traditional analyses of cyanobacterial presence. It is suggested that a surveillance protocol based on phycocyanin concentration can significantly improved the accuracy of the extent of cyanobacterial bloom development in the light of spatial and temporal variabilities associated with these occurrences.     

Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

High resolution direct-push profiling over short vertical distances was used to investigate CH(4) attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH(4) and CO(2), and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in δ(13)C(CH4) from an average of -57.6‰ (±1.7‰) in the methanogenic zone to -39.6‰ (±8.7‰) at 105m downgradient, strongly suggest CH(4) attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5m below the water table suggesting that transport of O(2) across the water table is leading to aerobic degradation of CH(4) at this interface. Dissolved N(2) concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O(2) through aerobic degradation of CH(4) or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O(2) rich recharge water were important O(2) transport mechanisms.     

Nitrate Leaching From a Mountain Forest Ecosystem with Gleysols Subjected to Experimentally Increased N Deposition

Nitrate leaching was measured over seven years of nitrogen (N) addition in a paired-catchment experiment in Alptal, central Switzerland (altitude: 1200 m, bulk N deposition: 12 kg ha^-1 a^-1). Two forested catchments (1500 m² each) dominated by Picea abies) were delimited by trenches in the Gleysols. NH₄NO₃ was added to one of the catchments using sprinklers. During the first year, the N addition was labelled with ¹⁵N. Additionally, soil N transformationswere studied in replicated plots. Pre-treatment NO₃ ^--N leaching was 4 kg ha^-1 a^-1 from both catchments, and remained between 2.5 and 4.8 kg ha^-1 a^-1 in the control catchment. The first year of treatment induced an additional leaching of 3.1 kg ha^-1, almost 90% of which was labelled with ¹⁵N, indicating that it did not cycle through the large N pools of the ecosystem (soil organic matter and plants). These losses partly correspond to NO₃ ^- from precipitation bypassing the soil due to preferential flow. During rain or snowmelt events, NO₃ ^- concentration peaks as the water table is rising, indicating flushing from the soil. Nitrification occurs temporarily along the water flow paths in the soil and can be the source of NO₃ ^- flushing. Its isotopic signature however, shows that this release mainly affects recently applied N, stored only between runoff events or up to a few weeks. At first, the ecosystem retained 90% of the added N (2/3 in the soil), but NO₃ ^- losses increased from 10 to 30% within 7 yr, indicating that the ecosystem became progressively N saturated.     

Dynamics of atmospheric nitrogen deposition in a temperate calcareous forest soil

In temperate forest ecosystems, soil acts as a major sink for atmospheric N deposition. A (15)N labeling experiment in a hardwood forest on calcareous fluvisol was performed to study the processes involved. Low amounts of ammonium ((15)NH(4)(+)) or nitrate ((15)NO(3)(-)) were added to small plots. Soil samples were taken after periods ranging from 1 h to 1 yr. After 1 d, the litter layer retained approximately 28% of the (15)NH(4)(+) tracer and 19% of (15)NO(3)(-). The major fraction of deposited N went through the litter layer to reach the soil within the first hours following the tracer application. During the first day, a decrease in extractable (15)N in the soil was observed ((15)NH(4)(+): 50 to 5%; (15)NO(3)(-): 60 to 12%). During the same time, the amount of microbial (15)N remained almost constant and the (15)N immobilized in the soil (i.e., total (15)N recovered in the bulk soil minus extractable (15)N minus microbial (15)N) also decreased. Such results can therefore be understood as a net loss of (15)N from the soil. Such N loss is probably explained by NO(3)(-) leaching, which is enhanced by the well-developed soil structure. We presume that the N immobilization mainly occurs as an incorporation of deposited N into the soil organic matter. One year after the (15)N addition, recovery rates were similar and approximately three-quarters of the deposited N was recovered in the soil. We conclude that the processes relevant for the fate of atmospherically deposited N take place rapidly and that N recycling within the microbes-plants-soil organic matter (SOM) system prevents further losses in the long term.     

Evaluation of the exposure methodology for risk-benefit assessment of seafood consumption

This study evaluated the methodology of using existing, international data to calculate the intake of nutrients and contaminants via seafood consumption on a national level. This was done by combining French seafood consumption data with two different datasets. The results showed that a significant correlation was found between the results obtained by using different data sets and that a high percentage of the population was classified in the same category (above or below the intake reference values). As such, the general conclusion that can be drawn from the results: 'whether a part of the population does exceed the toxicological reference values for certain contaminants and whether a part of the population does not reach the recommended intake for certain nutrients' remains the same for the two approaches. Therefore, it can be concluded that the existing, international probability distributions are useful when aiming to perform a cost-effective risk benefit evaluation of seafood consumption on national or regional level. When this evaluation does indicate that more detailed results are needed because a certain health risk exists, it can be decided that it is worth to spend more time and money for the analyses of national samples in order to collect more detailed results.