Cement/clay interactions-- a review: experiments, natural analogues, and modeling

The concept of storing radioactive waste in geological formations calls for large quantities of concrete that will be in contact with the clay material of the engineered barriers as well as with the geological formation. France, Switzerland and Belgium are studying the option of clayey geological formations. The clay and cement media have very contrasted chemistries that will interact and lead to a degradation of both types of material. The purpose of this review is to establish an exhaustive list of laboratory experiments so as to identify the reaction sequences in the evolution of both the clay minerals and accessory minerals during their alteration in an alkaline environment. We review the data on clay dissolution kinetics in this environment, and include an invaluable study of natural analogues that allow one to correlate the phenomena in time. The available data and experiments make it possible to construct predictive numerical models. However, as the quality of the data is inhomogeneous, we recommend a continuation of the thermodynamic and kinetic data acquisition. It is obvious that the numerical modeling of the alkaline disturbance will be more relevant if it can combine the advantages of the different detailed models: mineralogical completeness, combined modeling of the clay and cement media, evolution of the porosity, consideration of the pCO2 and all the surface reactions.     

Evaluation of aerated biofilter systems for microbial methane oxidation of poor landfill gas

In the long-term, landfills are producing landfill gas (LFG) with low calorific values. Therefore, the utilization of LFG in combined heat and power plants (CHP) is limited to a certain period of time. A feasible method for LFG treatment is microbial CH(4) oxidation. Different materials were tested in actively aerated lab-scale bio-filter systems with a volume of 0.167 m(3). The required oxygen for the microbial CH(4) oxidation was provided through perforated probes, which distributed ambient air into the filter material. Three air input levels were installed along the height of the filter, each of them adjusted to a particular flow rate. During the tests, stable degradation rates of around 28 g/(m(3) h) in a fine-grained compost material were observed at a CH(4) inlet concentration of 30% over a period of 148 days. Compared with passive (not aerated) tests, the CH(4) oxidation rate increased by a factor of 5.5. Therefore, the enhancement of active aeration on the microbial CH(4) oxidation was confirmed. At a O(2)/CH(4) ratio of 2.5, nearly 100% of the CH(4) load was decomposed. By lowering the ratio from 2.5 to 2, the efficiency fell to values from 88% to 92%. By varying the distribution to the three air input levels, the CH(4) oxidation process was spread more evenly over the filter volume.     

Bioconversion of selenate in methanogenic anaerobic granular sludge

The capacity of anaerobic granular sludge to remove selenate from contaminated wastewater was investigated. The potential of different types of granular sludge to remove selenate from the liquid phase was compared to that of suspended sludge and contaminated soil and sediment samples. The selenate removal rates ranged from 400 to 1500 microg g VSS(-1) h(-1), depending on the source of biomass, electron donor, and the initial selenate concentration. The granular structure protects the microorganisms when exposed to high selenate concentrations (0.1 to 1 mM). Anaerobic granular sludge "Eerbeek," originating from a UASB reactor treating paper mill wastewater, removed about 90, 50, and 36% of 0.1, 0.5, and 1 mM of Se, respectively, from the liquid phase when incubated with 20 mM lactate at 30 degrees C and pH 7.5. Selenite, elemental Se (Se(o)), and metal selenide precipitates were the conversion products. Enrichments from the anaerobic granular sludge "Eerbeek" were able to convert 90% of the 10-mM selenate to Se(o) at a rate of 1505 microg Se(VI) g cells(-1) h(-1), a specific growth rate of 0.0125 g cells h(-1), and a yield of 0.083 g cells mg Se(-1). Both microbial metabolic processes (e.g dissimilatory reduction) as well as microbially mediated physicochemical mechanisms (adsorption and precipitation) contribute to the removal of selenate from the Se-containing medium.     

Effects of elevated atmospheric carbon dioxide on biomass and carbon accumulation in a model regenerating longleaf pine community

Plant species vary in response to atmospheric CO2 concentration due to differences in physiology, morphology, phenology, and symbiotic relationships. These differences make it very difficult to predict how plant communities will respond to elevated CO2. Such information is critical to furthering our understanding of community and ecosystem responses to global climate change. To determine how a simple plant community might respond to elevated CO2, a model regenerating longleaf pine community composed of five species was exposed to two CO2 regimes (ambient, 365 micromol mol(-1) and elevated, 720 micromol mol(-1)) for 3 yr. Total above- and belowground biomass was 70 and 49% greater, respectively, in CO2-enriched plots. Carbon (C) content followed a response pattern similar to biomass, resulting in a significant increase of 13.8 Mg C ha(-1) under elevated CO2. Responses of individual species, however, varied. Longleaf pine (Pinus palustris Mill.) was primarily responsible for the positive response to CO2 enrichment. Wiregrass (Aristida stricta Michx.), rattlebox (Crotalaria rotundifolia Walt. Ex Gmel.), and butterfly weed (Asclepias tuberosa L.) exhibited negative above- and belowground biomass responses to elevated CO2, while sand post oak (Quercus margaretta Ashe) did not differ significantly between CO2 treatments. As with pine, C content followed patterns similar to biomass. Elevated CO2 resulted in alterations in community structure. Longleaf pine comprised 88% of total biomass in CO2-enriched plots, but only 76% in ambient plots. In contrast, wiregrass, rattlebox, and butterfly weed comprised 19% in ambient CO2 plots, but only 8% under high CO2. Therefore, while longleaf pine may perform well in a high CO2 world, other members of this community may not compete as well, which could alter community function. Effects of elevated CO2 on plant communities are complex, dynamic, and difficult to predict, clearly demonstrating the need for more research in this important area of global change science.     

Estimates of residual dairy manure nitrogen availability using various techniques

It is common practice to repeatedly apply dairy manure to the same fields. To accurately assess the total plant availability of manure nutrients, it is necessary to account for the nutrients remaining in soil from previous manure applications. A field experiment studying manure nitrogen (N) uptake by corn (Zea mays L.) was conducted from 1998 to 2003 on a Plano silt loam (fine-silty, mixed, mesic, Typic Argiudolls). Plots received two rates of semisolid manure either every year, every 2 yr, or every 3 yr to estimate first-, second-, and third-year dairy manure N residuals. Residual manure N availability was estimated from single and multiple manure applications using (i) the fertilizer N equivalence method, (ii) the apparent recovery (difference) method, (iii) relative effectiveness method, and (iv) recovery of (15)N-labeled manure. Second-year availabilities after a single manure application using the fertilizer equivalence, difference, and relative effectiveness methods were estimated to be 12, 8, and 4% of total manure N applications, respectively. Estimates of third-year availability by these methods were 3, 1, and 5%, respectively. Measurement of (15)N recovered from labeled manure was 6 and 2% in the second and third year, respectively. Fertilizer equivalence, difference, and relative effectiveness methods showed great year to year variability, reducing the confidence in the residual manure N availability estimates by these methods, but using (15)N-labeled manures reduced variability substantially. Based on this and other studies, we suggest that second- and third-year residual N availability from a single application of semisolid dairy manure would be 9 to 12%, and 3 to 5% of the original manure N application, respectively.     

Estimating plant-available nitrogen release from manures, composts, and specialty products

Recent adoption of national rules for organic crop production have stimulated greater interest in meeting crop N needs using manures, composts, and other organic materials. This study was designed to provide data to support Extension recommendations for organic amendments. Specifically, our objectives were to (i) measure decomposition and N released from fresh and composted amendments and (ii) evaluate the performance of the model DECOMPOSITION, a relatively simple N mineralization/immobilization model, as a predictor of N availability. Amendment samples were aerobically incubated in moist soil in the laboratory at 22 degrees C for 70 d to determine decomposition and plant-available nitrogen (PAN) (n = 44), and they were applied preplant to a sweet corn crop to determine PAN via fertilizer N equivalency (n = 37). Well-composted materials (n = 14) had a single decomposition rate, averaging 0.003 d(-1). For uncomposted materials, decomposition was rapid (>0.01 d(-1)) for the first 10 to 30 d. The laboratory incubation and the full-season PAN determination in the field gave similar estimates of PAN across amendments. The linear regression equation for lab PAN vs. field PAN had a slope not different from one and a y-intercept not different than zero. Much of the PAN released from amendments was recovered in the first 30 d. Field and laboratory measurements of PAN were strongly related to PAN estimated by DECOMPOSITION (r(2) > 0.7). Modeled PAN values were typically higher than observed PAN, particularly for amendments exhibiting high initial NH(4)-N concentrations or rapid decomposition. Based on our findings, we recommend that guidance publications for manure and compost utilization include short-term (28-d) decomposition and PAN estimates that can be useful to both modelers and growers.     

micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.     

Diuron in surface runoff and tile drainage from two grass-seed fields

The typical method of cool-season grass-seed production in Mediterranean climates briefly exposes surface waters to potentially high concentrations of the herbicide diuron [3-(3,4-dichlorophenyl)-1,1-dimethyl urea] during the initial season of growth. To better understand the process, and the degree, of diuron transport from agricultural fields, two grass-seed fields in the Willamette Valley of Oregon were monitored for diuron loss in surface runoff and tile drainage during the first wet season after planting. Initial diuron concentrations in surface runoff were high (>1000 microg L(-1) in one field and >100 microg L(-1) in the other), though they decreased by two orders of magnitude by the end of the season. Concentrations in the tile drains were as much as 1000 times lower than in the surface runoff during the first few weeks of runoff events, and they remained lower than surface water concentrations throughout the season. Total losses in surface runoff were between 1.3 and 3% of the amount applied-much higher than losses via the tile drains. It is also shown by means of a simple first-order decay model that, when little information is available, it may be best to describe diuron depletion in runoff water as a function of cumulative rainfall during the wet season.     

Nitrogen and phosphorus status of soils and trophic state of lakes associated with forage-based beef cattle operations in Florida

Forage-based livestock systems have been implicated as major contributors to deteriorating water quality, particularly for phosphorus (P) from commercial fertilizers and manures affecting surface and ground water quality. Little information exists regarding possible magnitudes of nutrient losses from pastures that are managed for both grazing and hay production and how these might impact adjacent bodies of water. We examined the changes that have occurred in soil fertility levels of rhizoma peanut (Arachis glabrata Benth.)-based beef cattle pastures (n = 4) in Florida from 1988 to 2002. These pastures were managed for grazing in spring followed by haying in late summer and were fertilized annually with P (39 kg P2O5 ha(-1)) and K (68 kg K2O ha(-1)). Additionally, we investigated trends in water quality parameters and trophic state index (TSI) of lakes (n = 3) associated with beef cattle operations from 1993 to 2002. Overall, there was no spatial or temporal buildup of soil P and other crop nutrients despite the annual application of fertilizers and daily in-field loading of animal waste. In fact, soil fertility levels showed a declining trend for crop nutrient levels, especially soil P (y = 146.57 - 8.14 x year; r2= 0.75), even though the fields had a history of P fertilization and the cattle were rotated into the legume fields. Our results indicate that when nutrients are not applied in excess, cow-calf systems are slight exporters of P, K, Ca, and Mg through removal of cut hay. Water quality in lakes associated with cattle production was "good" (30-46 TSI) based on the Florida Water Quality Standard. These findings indicate that properly managed livestock operations may not be major contributors to excess loads of nutrients (especially P) in surface water.