Influence of pH on the redox chemistry of metal (hydr)oxides and organic matter in paddy soils

Purpose

The primary purpose of this study was to determine how flooding and draining cycles affect the redox chemistry of metal (hydr)oxides and organic matter in paddy soils and how the pH influences these processes. Our secondary purpose was to determine to what extent a geochemical thermodynamic equilibrium model can be used to predict the solubility of Mn and Fe during flooding and draining cycles in paddy soils.

Material and methods

We performed a carefully designed column experiment with two paddy soils with similar soil properties but contrasting pH. We monitored the redox potential (Eh) continuously and took soil solution samples regularly at four depths along the soil profile during two successive flooding and drainage cycles. To determine dominant mineral phases of Mn and Fe under equilibrium conditions, stability diagrams of Mn and Fe were constructed as a function of Eh and pH. Geochemical equilibrium model calculations were performed to identify Mn and Fe solubility-controlling minerals and to compare predicted total dissolved concentrations with their measured values.

Results and discussion

Flooding led to strong Eh gradients in the columns of both soils. In the acidic soil, pH increased with decreasing Eh and vice versa, whereas pH in the alkaline soil was buffered by CaCO₃. In the acidic soil, Mn and Fe solubility increased during flooding due to reductive dissolution of their (hydr)oxides and decreased during drainage because of re-oxidation. In the alkaline soil, Mn and Fe solubility did not increase during flooding due to Mn(II) and Fe(II) precipitation as MnCO₃, FeCO₃, and FeS. The predicted levels of soluble Mn and Fe in the acidic soil were much higher than their measured values, but predictions and measurements were rather similar in the alkaline soil. This difference is likely due to kinetically limited reductive dissolution of Mn and Fe (hydr)oxides in the acidic soil. During flooding, the solubility of dissolved organic matter increased in both soils, probably because of reductive dissolution of Fe (hydr)oxides and the observed increase in pH.

Conclusions

Under alternating flooding and draining conditions, the pH greatly affected Mn and Fe solubility via influencing either reductive dissolution or carbonate formation. Comparison between measurements and geochemical equilibrium model predictions revealed that reductive dissolution of Mn and Fe (hydr)oxides was kinetically limited in the acidic soil. Therefore, when applying such models to systems with changing redox conditions, such rate-limiting reactions should be parameterized and implemented to enable more accurate predictions of Mn and Fe solubility.     

The impacts of roads and other infrastructure on mammal and bird populations: A meta-analysis

Biodiversity is being lost at an increased rate as a result of human activities. One of the major threats to biodiversity is infrastructural development. We used meta-analyses to study the effects of infrastructure proximity on mammal and bird populations. Data were gathered from 49 studies on 234 mammal and bird species. The main response by mammals and birds in the vicinity of infrastructure was either avoidance or a reduced population density. The mean species abundance, relative to non-disturbed distances (MSA), was used as the effect size measure. The impact of infrastructure distance on MSA was studied using meta-analyses. Possible sources of heterogeneity in the results of the meta-analysis were explored with meta-regression.Mammal and bird population densities declined with their proximity to infrastructure. The effect of infrastructure on bird populations extended over distances up to about 1 km, and for mammal populations up to about 5 km. Mammals and birds seemed to avoid infrastructure in open areas over larger distances compared to forested areas, which could be related to the reduced visibility of the infrastructure in forested areas. We did not find a significant effect of traffic intensity on the MSA of birds. Species varied in their response to infrastructure. Raptors were found to be more abundant in the proximity of infrastructure whereas other bird taxa tended to avoid it. Abundances were affected at variable distances from infrastructure: within a few meters for small-sized mammals and up to several hundred meters for large-sized mammals.Our findings show the importance of minimizing infrastructure development for wildlife conservation in relatively undisturbed areas. By combining actual species distributions with the effect distance functions we developed, regions sensitive to infrastructure development may be identified. Additionally, the effect distance functions can be used in models in support of decision making on infrastructure planning.     

Estimation of wood density and chemical composition by means of diffuse reflectance mid-infrared Fourier transform (DRIFT-MIR) spectroscopy

Sitka spruce (Picea sitchensis) samples (491) from 50 different clones as well as 24 different tropical hardwoods and 20 Scots pine (Pinus sylvestris) samples were used to construct diffuse reflectance mid-infrared Fourier transform (DRIFT-MIR) based partial least squares (PLS) calibrations on lignin, cellulose, and wood resin contents and densities. Calibrations for density, lignin, and cellulose were established for all wood species combined into one data set as well as for the separate Sitka spruce data set. Relationships between wood resin and MIR data were constructed for the Sitka spruce data set as well as the combined Scots pine and Sitka spruce data sets. Calibrations containing only five wavenumbers instead of spectral ranges 4000-2800 and 1800-700 cm(-1) were also established. In addition, chemical factors contributing to wood density were studied. Chemical composition and density assessed from DRIFT-MIR calibrations had R2 and Q2 values in the ranges of 0.6-0.9 and 0.6-0.8, respectively. The PLS models gave residual mean squares error of prediction (RMSEP) values of 1.6-1.9, 2.8-3.7, and 0.4 for lignin, cellulose, and wood resin contents, respectively. Density test sets had RMSEP values ranging from 50 to 56. Reduced amount of wavenumbers can be utilized to predict the chemical composition and density of a wood, which should allow measurements of these properties using a hand-held device. MIR spectral data indicated that low-density samples had somewhat higher lignin contents than high-density samples. Correspondingly, high-density samples contained slightly more polysaccharides than low-density samples. This observation was consistent with the wet chemical data.     

Harvesting fodder trees in montane forests in Kenya: species,techniques used and impacts

There has been an increasing interest in fodder trees and their potential to help the rural poor. However, few studies have addressed the ecological impacts of fodder tree harvesting. We investigated the species harvested and the techniques used, and the effects of fodder harvesting on (1) species’ populations and (2) forest carbon stocks in three montane forests in Kenya. Focus-group discussions were organized in 36 villages to determine which species were harvested and with which techniques. Field observations were made on vegetation plots: stem diameter, tree height, species and extent of harvest were recorded. Carbon stocks were calculated using an allometric equation with (1) observed height of harvested trees, and (2) potential height estimated with a power model, and results were compared. Eight tree species were commonly harvested for fodder using different techniques (some branches, main stem, most branches except stem apex). Fodder harvesting (together with other uses for some species) negatively affected one species populations (Olea europaea), it did not negatively affect four (Drypetes gerrardii, Gymnosporia heterophylla, Pavetta gardeniifolia, Xymalos monospora), and more information is needed for three species (Olea capensis, Prunus africana, Rinorea convallarioides). Fodder harvesting did not significantly reduce forest carbon stocks, suggesting that local communities could continue using these fodder trees if a carbon project is established. Among the fodder species studied, X. monospora could be used in reforestation programs, as it has multiple uses and can withstand severe pruning. Although our study is only a snapshot, it is a baseline which can be used to monitor changes in fodder harvesting and its impacts related to increasing droughts in northern Kenya and increasing human populations.     

Leaching of pesticides and a bromide tracer through lysimeters from five contrasting soils

In each of two seasons, undisturbed lysimeters 0.8 m in diameter and 1.05 m in length taken from five soil types were cropped with winter wheat. They received autumn applications of the pesticides isoproturon and linuron as well as a bromide tracer and spring applications of dimethoate and MCPA. Leachate was collected at regular intervals and concentrations of the various solutes determined. Rainfall from December to March was 290 and 191 mm in the first and second seasons, respectively. Both springs were exceptionally dry with less than 50% of the mean April‐to‐June rainfall of 138 mm. Total flow from the lysimeters ranged from 335 to 477 mm (and from 0.78 to 3.95 pore volumes) over the two seasons. Leaching to drainage of bromide highlighted soils where preferential flow was influential with total losses ranging from 24% of applied for a strongly structured, alluvial clay loam to 79% for an unstructured sand. Leaching to drainage of isoproturon (K_oc ≈ 100 ml g⁻¹) was observed from all but a peat soil with losses greater (0.31–1.01% of applied) from the clay loam and a deep medium loam, where patterns of leaching clearly indicated preferential flow mechanisms, than from the sand and a light loam over gravel (0.04–0.18% of applied) where a broad breakthrough curve indicated that matrix flow was more important. Linuron (K_oc ≈ 500 ml g⁻¹) was detected in occasional samples of leachate from the clay loam, the light loam over gravel and the medium loam during the first season only (maximum loss 0.12% of applied). The sandy soil, often considered most vulnerable to leaching, gave the smallest total losses of pesticide of the four mineral soils, whilst significant preferential flow in the deep, medium loam was believed to result from a compacted topsoil. Neither of the spring‐applied pesticides was detected in the leachate, as flow following application was very small and relatively slow. © 2000 Society of Chemical Industry     

Evaluating the Performance of Gluten ELISA Test Kits: The Numbers Do Not Tell the Tale

A wide variety of enzyme‐linked immunosorbent assays (ELISAs) are commercially available for gluten detection in food, including new formats and assays with antibodies against relevant gluten epitopes. Nevertheless, problems persist to accurately determine the gluten content of products. In this study, the performance of a set of 14 ELISA kits for gluten detection, representative of the current ELISA methods available on the market, was evaluated. These tests were used to determine gluten content in a series of relevant food matrices varying in complexity. Our results show that, currently, there is no single ELISA method that can accurately detect and quantify gluten in all different matrices. This includes the current type I method R5 as recommended by Codex Alimentarius. We conclude that further improvements are urgently needed and recommend focusing on competitive formats, improving extraction methods, and the detection of relevant gluten peptides (in order of priority).