Currently, few studies have revealed the comprehensive effects of environmental organic matter, freeze–thaw and oxidative aging on the adsorption performance of cadmium (Cd(II)), which is essential for the sustainable stability evaluation of the adsorbent. Herein, we observed that humic acids (HAs) extracted from different soils inhibited the adsorption performance of Cd(II) onto the cuttlebone-derived samples by occupying the different major adsorption active sites of the adsorbent, and the lower cadmium-complexation ability of HAs would increase the occupation of adsorption sites. The freeze–thaw process increased the pore size and volume of the cuttlebone-derived samples, while oxidative aging enhanced the specific surface area and introduced additional C–O/C=O groups. These changes promoted the adsorption performance of Cd(II) in the cuttlebone-derived samples after freeze–thaw or oxidative aging. Additionally, the resistances of cuttlebone-based adsorbents to HAs, freeze–thaw, and oxidative aging were elucidated and optimized by simple alkali boiling or carbonization treatment. Furthermore, the adsorption capacities of Cd(II) by samples in the natural cadmium-contaminated river ranged from 548.99 mg g−1 to 571.55 mg g−1, which are higher values than those of most reported adsorbents. Therefore, this work provides an important experimental basis for the practical application and sustainable design of adsorbents under real environmental conditions.
With the frequent occurrence of global droughts, modified biochar has demonstrated the potential to be an efficient soil amendment, which could affect carbon and nitrogen sequestration in arid soil. Therefore, this study investigated the co-application of pristine biochar (BC), Fe-modified biochar (FB) and H2O2-modified biochar (HB) with green manure during a 70-day laboratory incubation under drought conditions and normal moisture conditions. The emissions were quantified using gas chromatography, while microbial necromass carbon and nitrogen were measured by quantifying the amino sugar content by gas chromatography–mass spectrometry, and other soil carbon and nitrogen fractions were determined through chemical analysis. The results revealed that under drought conditions, compared to BC co-application with green manure, the total carbon loss of FB and HB co-application with green manure was reduced from 24.38% to 13.14% and 14.27%, respectively, and the total nitrogen loss was also reduced from 14.61% to 7.23% and 7.27%, respectively. This reduction occurred because FB and HB protected soil organic matter through iron oxide binding and micropore adsorption, thereby increasing the content of soil total humus acid (>5%) and microbial necromass nitrogen (>16%). In addition, under normal moisture conditions, BC, FB and HB co-application with green manure enhanced microbial activity and promoted the formation of stable total humus acid, thereby enhancing carbon and nitrogen sequestration. In conclusion, this study provides crucial theoretical support for the optimization of the green manure return via modified biochar co-application in arid environments.
The impact of biochar on N conversion in drought-affected soil with green manure application has not been systematically investigated. Therefore, this study examined the effects of biochar produced at 350 °C, 550 °C, and 750 °C (BC350, BC550, and BC750) on green manure (Medicago sativa L.) decomposition and N turnover in soil (Hapli-Udic Ferralosol) during a 60-day laboratory incubation experiment under different moisture conditions (45% or 65% soil water-holding capacity (WHC)). Due to low-temperature biochar (BC350) possessing hydrophilicity (thereby enhancing water retention) due to its surface oxygen-containing functional groups, while high-temperature biochar (BC750) relies on the aromatic conjugated π-electron system for electron transfer, both BC350 and BC750 promoted green manure decomposition and mineralization. Compared with green manure alone, co-application of BC350 and BC750 with green manure increased soil NH4+–N content by 5.58% and 38.37%, respectively. However, a significant total N loss (>11%) occurred under drought conditions. Partial least squares path modeling was used to elucidate the key driving pathways related to C and N sequestration in drought-affected soil with green manure and biochar co-application. The results indicate that the enhanced soil N loss could be attributed to both the biochar-induced rise in soil pH (>8%) and the drought-driven suppression of stable organic matter (e.g., >20% reduction in humus acid) and macroaggregate formation. This study demonstrates that although biochar addition can promote the decomposition of green manure to release available N, it may also exacerbate total soil N loss. Only under normal moisture conditions can the N released from green manure be converted into humus-associated N.