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.     

Man-made chemicals found in remote areas of the world: the experimental definition for POPs

Members of the United Nations Economic Commission for Europe (UN-ECE) signed a legally binding protocol on persistent organic pollutants (POPs) in February 1998 under the Convention on Long-Range Transboundary Air Pollution. A treaty that intends to control the production, import, export, disposal and use of toxic chemicals that persist for decades in the environment has been formally signed at a conference in May 2001 in Stockholm. The 2001 POP treaty, like the 1998 LRTAP POP protocol, contains a provision on adding further chemicals to the initial group of twelve or fifteen. The occurrence of a compound or a group of compounds in so called remote and pristine areas, e.g. in the Artic or in the Southern Hemisphere, proves its stability under the chemical and biological conditions of the environment. Compounds identified in this way, in samples taken primarily in very remote regions of the planet, are classified by their environmental fate and global distribution as persistent organic pollutants (POPs), regardless of any political assessments.     

Anionic polyacrylamide effects on soil sorption and desorption of metolachlor,atrazine, 2,4-D,and picloram

Polyacrylamide (PAM) treatment of irrigation water is a growing conservation technology in irrigated agriculture in recent years. There is a concern regarding the environmental impact of PAM after its application. The effects of anionic PAM on the sorption characteristics of four widely used herbicides (metolachlor, atrazine, 2,4-D, and picloram) on two natural soils were assessed in batch equilibrium experiments. Results showed that PAM treatment kinetically reduced the sorption rate of all herbicides, possibly due to the slower diffusion of herbicide molecules into interior sorption sites of soil particles that were covered and/or cemented together by PAM. The equilibrium sorption and desorption amounts of nonionic herbicides (metolachlor and atrazine) were essentially unaffected by anionic PAM, even under a high PAM application rate, while the sorption amounts of anionic herbicides (2,4-D and picloram) were slightly decreased and their desorption amounts increased little. The impact mechanisms of PAM were related to the molecular characteristics of PAM and herbicides. The negative effects of PAM on the sorption of anionic herbicides are possibly caused by the enhancement of electrostatic repulsion by presorbed anionic PAM and competition for sorption sites. However, steric hindrance of the large PAM molecule weakens its influence on herbicide sorption on interior sorption sites of soil particles, which probably leads to the small interference on herbicide sorption, even under high application rates.     

Modeling pollutant release from a surface source during rainfall runoff

Though runoff from manure spread fields is recognized as an important mode of nonpoint-source pollution, there are no models that mechanistically describe transport from a field-spread manure-type source. A mechanistic, physically based model for pollutant release from a surface source, such as field-spread manure, was hypothesized, laboratory tested, and field-applied. The primary objective of this study was to demonstrate the potential applicability of a mechanistic model to pollutant release from surface sources. The laboratory investigation used stable sources and a conservative "pollutant" (KCl) so that the dynamic effects of source dissolution and chemical transformations could be ignored and transport processes isolated. The field investigation used runoff and soluble reactive phosphorus (SP) data collected from a dairy-manure-spread field in the Cannonsville watershed in the Catskills region of New York State. The model predictions corroborated well with observations of runoff and pollutant delivery in both the laboratory and the field. "Pollutant" release from surface sources was generally predicted within 11% of laboratory KCl measurements and field SP observations. Laboratory flume runoff predictions with 15 and 26% errors for 25 and 15 mm h(-1) simulated rainfall intensity experiments, respectively, represented root mean square errors of less than 0.2 mLs(-1). A 26% error was calculated for overland flow predictions in the field, which translated into approximately a 39 mLs(-1) error. Results suggest that the hypothesized model satisfactorily represents the primary mechanisms in pollutant release from surface sources.