Evaluation of the diffusive gradients in thin-films (DGT) technique for measuring nitrate and ammonium in soil

Abstract

Environmental context Nitrate (NO3−) and ammonium (NH4+) are the most important soil nitrogen forms for plant growth. However, conventional extraction techniques may introduce artefacts affecting the measurement of plant-available N concentrations following sampling and sample preparation processes. This is the first study of the DGT technique being used to measure NO3-N and NH4-N in a wide range of soils, compared with conventional KCl extraction, and examined different factors that contribute to the plant-availability of these ions in soils. The knowledge would help to optimise soil nitrogen management practices, increase economic benefits and reduce environmental impacts. Rationale The availability of soil nitrogen for plant uptake can be affected by numerous soil factors such as soil texture, moisture and organic matter content, temperature and microbial activity. Conventional extraction techniques may affect the measurement of plant-available N concentrations following sampling and sample preparation processes, including drying, sieving, homogenising, freezing and thawing. The diffusive gradients in thin-films (DGT) technique can overcome some limitations of the conventional extraction techniques and has been used to successfully estimate the plant-available fractions of nutrients, such as P, K, Zn, Cu and Mn in soils. Therefore, it is important to evaluate the use of DGT for measuring NO3− and NH4+ in a wide variety of soils and examine the factors that contribute to the plant-availability of these ions in soils. Methodology The experiment evaluated the ability of the DGT technique to measure NO3-N and NH4-N in soils using binding layers containing A520E anion exchange resin or Microlite® PrCH cation exchange resin, respectively. The DGT results were compared to those from conventional KCl extraction. Results The A520E- and PrCH-DGTs showed good detection limits for NO3-N (6.90 µg L−1) and NH4-N (6.23 µg L−1) and were able to measure potentially available NO3-N and NH4-N in unfertilised soils. The mass of NO3-N and NH4-N that accumulated on the DGT device increased linearly across soil concentrations ranging from 5 to 300 mg kg−1 NO3-N (depending on soil type) and 5–300 mg kg−1 NH4-N; which is equivalent to fertiliser rates of 75–450 kg ha−1 N. DGTs were used to measure potentially available NO3-N and NH4-N in ten soils with various physical and chemical properties. The DGT results were compared with conventional KCl extraction used to determine soil mineral N. DGT and KCl extraction measured values were significantly correlated with each other for NO3-N (R2 = 0.53; P-value < 0.001), but the relationship between the two measurements was weaker for NH4-N (R2 = 0.20, P-value = 0.045). Discussion The results suggest that the two methods sample different N pools in the soils, with DGT targeting the NO3-N and NH4-N that are available in soil pore water and attached to labile solid phases.