Superabsorbent polymers (SAP) are used, inter alia, as soil amendment to increase the water holding capacity of soils. Biodegradability of soil conditioners has become a desired key characteristic to protect soil and groundwater resources. The present study characterized the biodegradability of one acrylate based SAP in four agricultural soils and at three temperatures. Mineralisation was measured as the (13)CO₂ efflux from (13)C-labelled SAP in soil incubations. The SAP was either single-labelled in the carboxyl C-atom or triple-labelled including additionally the two C-atoms interlinked in the SAP backbone. The dual labelling allowed estimating the degradation of the polyacrylate main chain. The (13)CO₂ efflux from samples was measured using an automated system including wavelength-scanned cavity ring-down spectroscopy. Based on single-labelled SAP, the mean degradation after 24 weeks varied between 0.45% in loamy sand and 0.82% in loam. However, the differences between degradation rates in different soils were not significant due to a large intra-replicate variability. Similarly, mean degradation did not differ significantly between effective temperature regimes of 20° and 30 °C after 12 weeks. Results from the triple-labelled SAP were lower as compared to their single-labelled variant. Detailed results suggest that the polyacrylate main chain degraded in the soils, if at all, at rates of 0.12-0.24 % per 6 months.
A system was developed for the automatic measurements of ¹³CO₂ efflux to determine biodegradation of extra carbon amendments to soils. The system combines wavelength-scanned cavity ring down laser spectroscopy (WS-CRDS) with the open-dynamic chamber (ODC) method. The WS-CRDS instrument and a batch of 24 ODC are coupled via microprocessor-controlled valves. Determination of the biodegradation requires a known δ¹³C value and the applied mass of the carbon compounds, and the biodegradation is calculated based on the ¹³CO₂ mixing ratio (ppm) sampled from the headspace of the chambers. The WS-CRDS system provided accurate detection based on parallel samples of three standard gases (¹³CO₂ of 2, 11 and 22 ppm) that were measured simultaneously by isotope ratio mass spectrometry (linear regression R² = 0.99). Repeated checking with the same standards showed that the WS-CRDS system showed no drift over seven months.The applicability of the ODC was checked against the closed static chamber (CSC) method using the rapid biodegradation of cane sugar-δ¹³C-labeled through C4 photosynthesis. There was no significant difference between the results from 7-min ODC and 120-min CSC measurements. Further, a test using samples of either cane sugar (C4) or beetroot sugar (C3) mixed into standard soil proved the target functionality of the system, which is to identify the biodegradation of carbon sources with significantly different isotopic signatures.
Biodegradability is a desired characteristic for synthetic soil amendments. Cross-linked polyacrylic acid (PAA) is a synthetic superabsorbent used to increase the water availability for plant growth in soils. About 4% within products of cross-linked PAA remains as linear polyacrylic acid (PAAlinear). PAAlinear has no superabsorbent function but may contribute to the apparent biodegradation of the overall product. This is the first study that shows specifically the biodegradation of PAAlinear in agricultural soil. Two (13)C-labeled PAAlinear of the average molecular weights of 530, 400, and 219,500 g mol(-1) were incubated in soil. Mineralization of PAAlinear was measured directly as the (13)CO2 efflux from incubation vessels using an automatic system, which is based on (13)C-sensitive wavelength-scanned cavity ring-down spectroscopy. After 149 days, the PAAlinear with the larger average molecular weight and chain length showed about half of the degradation (0.91% of the initial weight) of the smaller PAAlinear (1.85%). The difference in biodegradation was confirmed by the δ(13)C signature of the microbial biomass (δ(13)Cmic), which was significantly enriched in the samples with short PAAlinear (-13‰ against reference Vienna Pee Dee Belemnite,VPDB) as compared to those with long PAAlinear (-16‰ VPDB). In agreement with other polymer studies, the results suggest that the biodegradation of PAAlinear in soil is determined by the average molecular weight and occurs mainly at terminal sites. Most importantly, the study outlines that the size of PAA that escapes cross-linking can have a significant impact on the overall biodegradability of a PAA-based superabsorbent.
Suitable predictors of degradability are sought to support the identification of biochars with large potential to increase C sequestration in soils. We determined the biodegradation of 9 chars from hydrothermal carbonization and pyrolysis in two agricultural soils. The 200-and 115-day degradation correlated strongly with the O:C-and slightly with the H:C-atomic ratio of 9 and 14 biochars, respectively. Highest temperature treatment and ash content did not show similar correlations.
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