Automated and continuous redox potential measurements in soil

Redox potential (Eh) describes the electrical state of a matrix. In soils, Eh is an important parameter controlling the persistence of many organic and inorganic compounds. A popular, but also criticized, manual measuring method makes use of a small tip of Pt placed on a copper wire that is placed in the soil; a reference electrode is placed in the same soil at a fixed distance. Fluctuations in redox potential values measured in the soil can be very large and depth-dependent. This will be overlooked when making single-point measurements. We developed the datalogger Hypnos 2.0 for continuous redox potential and temperature measurements at various depths in the soil and without disturbance of the site. Hypnos is field-deployable, relatively cheap, and runs on batteries. The datalogger can use a "sleep mode" between sampling events. In sleep mode, there is no constant voltage on the Pt wire or the reference electrode, but there is only a short pulse during sampling. We did not measure an effect of this short pulse on the measured redox potential. In sandy soils in mesocosms and in a salt marsh soil we measured changes in the Eh as large as from -400 to +100 mV within 4 d, and daily cycles of 200 mV. Both absolute redox potential values and their diurnal variations were depth-dependent. Because single redox measurements are insufficient in describing redox conditions in some soil systems, Hypnos can be a powerful tool when studying the effects of fluctuating redox conditions on metal availability and pollutant degradation.     

The contemporary Oceania zinc cycle: one-year stocks and flows

The material flow approach provides a framework from which to address resource management and estimate gross environmental impacts, both spatially and temporally. In this article, the major flows of zinc in Oceania over its entire life-cycle are examined; these include production (mining, milling, and refining), fabrication and manufacturing of semi- and finished products, use, and the waste management system. Comprehensive mass balances were applied to determine the zinc flows, including the quantities of zinc entering stocks in waste and in-use reservoirs. The Oceania cycle shows that substantial amounts of zinc (about 1120Gg/year) are mined on the continent. The total flow of zinc in finished products entering the use stage is about 8.6kg/(capita.year), substantially exceeding the zinc flow in discarded products. This difference, about 7.2kgZn/(capita.year) on average, is added to the in-use reservoir, largely for galvanizing applications in domestic construction and transportation. Less than 60% of all discarded zinc entering the waste management system is recycled. Much of the remaining discarded zinc is diluted into other waste streams, where recovery and recycling are probably not economically feasible.     

Spiking of performance reference compounds in low density polyethylene and silicone passive water samplers

A method for spiking performance reference compounds (PRCs) into low density polyethylene (LDPE) and silicone polymers is described. This method is based on equilibration of the polymers in aqueous/methanolic solutions of PRCs. Equilibration times range from minutes to hours for perdeuterated polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) with a hydrophobicity in the range 3.9 < logKow < 7.7. Best results were obtained for methanol-water ratios of 80/20 (v/v). The method allows for the use of PRCs for in situ calibration of the uptake kinetics of these solvent-free sampling phases in a similar way as for semipermeable membrane devices (SPMDs).     

Characterization of the leaching behaviour of concrete mortars and of cement-stabilized wastes with different waste loading for long term environmental assessment

The leaching behaviour of cement-based products-both construction products and cement-stabilized wastes--have been shown to be similar after assessing the leaching characteristics by means of a pH dependence leaching test. This procedure is particularly suited to identifying the chemical speciation of materials. Geochemical modelling has shown a number of solubility controlling phases in this largely inorganic matrix, that can very well explain the observed leaching patterns as a function of pH. Understanding these relationships allows the prediction of leaching behaviour under other exposure conditions and to improve the ultimate quality of products, if so desired. The role of ettringite-type phases for the binding of oxyanions in the pH range above pH 12 has been identified before and confirmed in this work. The order of incorporation follows from the ratio between the maximum leachability at mildly alkaline pH and at high pH. Increased levels of sulfate negatively influence the binding of oxyanions in cement-stabilized waste through site competition.     

Dissolution kinetics of heavy metals in Dutch carbonate- and sulfide-rich freshwater sediments

In two sulfide-rich freshwater sediments from the Biesbosch and Kromme Rijn River in the Netherlands differing in carbonate content and acid volatile sulfide (AVS) content, metal and sulfide dissolution kinetics were studied at different acid concentrations by varying both the procedure of acid addition and the extraction time. The establishment of equilibrium was monitored by measuring the pH in time, which reached a near constant value. The equilibrium pH was reached quickly when large amounts of acid were added and slowly when small amounts of acid were added. This observation was confirmed by the yield of extracted metals after either a 45-min or 24-h extraction over a pH range from 0 to 5. The pH factor seemed to be of more influence than time for the dissolution of metals. The amount of extracted metals was highly dependent on the metal itself due to its physico-chemical behavior. Although the sediments studied varied in carbonate content, acid volatile sulfide (AVS), and total metal content, the extracted fraction of metals compared with their total content in the sediment was similar for most metals. Finally, the AVS content as well as the ratio of simultaneously extracted metals (SEM; sum of Cd, Cu, Ni, Pb, and Zn) to AVS decreased with increasing pH. Because the SEM to AVS ratio may be used to set environmental quality criteria for the sediment compartment, this observation is of significance.     

Effects of soil variability and weather conditions on pesticide leaching--a farm-level evaluation

In line with European regulations, Dutch law imposes an environmental threshold of 0.1 microg L(-1) on pesticide concentrations in ground water. During registration, the risk of exceeding this threshold is assessed through simulations for one or a few standard scenarios that do not reflect spatial variability under field conditions. The introduction of precision agriculture, where soil variability is actively managed, can increase control over pesticide leaching. This study presents a step-wise evaluation of the effects of soil variability and weather conditions on pesticide leaching. The evaluation was conducted on a 100-ha arable farm and aimed at identifying opportunities for precision management. As a first step, a relative risk assessment identified pesticides presenting a relatively high risk to the environment. Second, the effect of weather conditions was analyzed through 20 years of simulations for three distinct soil profiles. Results were summarized in cumulative probability plots to provide a probabilistic characterization of historical weather data. The year matching 90% probability (1981) served as a reference to simulate pesticide leaching from 612 soil profiles. After interpolation, areas where concentrations exceeded the environmental threshold were identified. Out of a total of 19 pesticides, isoproturon [N-dimethyl-N'-(4-(1-methylethyl)phenyl)urea], metribuzin [4-amino-6-tert-butyl-3-(methylthio)-as-triazin-5(4H)-one], and bentazon [2,1,3-benzothiadiazin-4(3H)-one, 3-isopropyl-, 2,2-dioxide] showed the highest risk for leaching. Leaching was strongly affected by soil variability at the within-field, field, and farm levels. Opportunities for precision management were apparent, but depended on the scale level at which environmental thresholds were implemented. When legislation is formulated in this issue, the presented step-wise evaluation can serve as a basis for identification and precision management of high-risk pesticides.     

The effect of nitrogen enrichment on the carbon sink in coniferous forests: Uncertainty and sensitivity analyses of three ecosystem models

Estimates of the global carbon sink induced by nitrogen enrichment range vary widely, from nearly zero to 2.3 Gt C year^?1. It is necessary to reduce this uncertainty if we are to make accurate predictions of the future magnitude of the terrestrial carbon sink. Here, we present a Monte Carlo approach to uncertainty and sensitivity analysis of three ecosystem models, Century, BGC and Hybrid. These models were applied to a coniferous forest ecosystem in Sweden. The best estimate of the change in total carbon content of the ecosystem with the cumulative change in nitrogen deposition over 100 years, ΔC_total/ΔN_deposition was 20.1 kg C (kg N)^?1 using the pooled mean, with a pooled standard deviation of 13.8 kg C (kg N)^?1. Variability in parameters accounted for 92% of the total uncertainty in ΔC_total/ΔN_deposition, and only 8% was attributable to differences between models. The most sensitive parameters were those which controlled the allocation of assimilate between leaves, roots and stem. In particular, an increase in allocation to fine roots led to a large reduction in ΔC_total/ΔN_deposition in all models, because the fine roots have a very high turnover rate, and extra carbon allocated there is soon lost through mortality and decomposition.     

Land application of domestic effluent onto four soil types: plant uptake and nutrient leaching

Land application has become a widely applied method for treating wastewater. However, it is not always clear which soil-plant systems should be used, or why. The objectives of our study were to determine if four contrasting soils, from which the pasture is regularly cut and removed, varied in their ability to assimilate nutrients from secondary-treated domestic effluent under high hydraulic loadings, in comparison with unirrigated, fertilized pasture. Grassed intact soil cores (500 mm in diameter by 700 mm in depth) were irrigated (50 mm wk(-1)) with secondary-treated domestic effluent for two years. Soils included a well-drained Allophanic Soil (Typic Hapludand), a poorly drained Gley Soil (Typic Endoaquept), a well-drained Pumice Soil formed from rhyolitic tephra (Typic Udivitrand), and a well-drained Recent Soil formed in a sand dune (Typic Udipsamment). Effluent-irrigated soils received between 746 and 815 kg N ha(-1) and 283 and 331 kg P ha(-1) over two years of irrigation, and unirrigated treatments received 200 kg N ha(-1) and 100 kg P ha(-1) of dissolved inorganic fertilizer over the same period. Applying effluent significantly increased plant uptake of N and P from all soil types. For the effluent-irrigated soils plant N uptake ranged from 186 to 437 kg N ha(-1) yr(-1), while plant P uptake ranged from 40 to 88 kg P ha(-1) yr(-1) for the effluent-irrigated soils. Applying effluent significantly increased N leaching losses from Gley and Recent Soils, and after two years ranged from 17 to 184 kg N ha(-1) depending on soil type. Effluent irrigation only increased P leaching from the Gley Soil. All P leaching losses were less than 49 kg P ha(-1) after two years. The N and P leached from effluent treatments were mainly in organic form (69-87% organic N and 35-65% unreactive P). Greater N and P leaching losses from the irrigated Gley Soil were attributed to preferential flow that reduced contact between the effluent and the soil matrix. Increased N leaching from the Recent Soil was the result of increased leaching of native soil organic N due to the higher hydraulic loading from the effluent irrigation.