Patterns of δ15N in forest soils and tree foliage and rings between climate zones in relation to atmospheric nitrogen deposition: A review.

The stable nitrogen (N) isotope ratio (δ15N) of forest samples (soils, tree foliage, and tree rings) has been used as a powerful indicator to explore the responses of forest N cycling to atmospheric N deposition. This review investigated the patterns of δ15N in forest samples between climate zones in relation to N deposition. Forest samples exhibited distinctive δ15N patterns between climate zones due to differences in site conditions (i.e., N availability and retention capacity) and the atmospheric N deposition characteristics (i.e., N deposition rate, N species, and δ15N of deposited N). For example, the δ15N of soil and foliage was higher for tropical forests than for other forests by >1.2 ‰ and 4 ‰, respectively due to the site conditions favoring N losses coupled with relatively low N deposition for tropical forests. This was further supported by the unchanged or increased δ15N of tree rings in tropical forests, which contrasts with other climate zones that exhibited a decreased wood δ15N since the 1920s. Subtropical forests under a high deposition of reduced N (NHy) had a lower δ15N by 2-5 ‰ in the organic layer compared with the other forests, reflecting high retention of 15N-depleted NHy deposition. At severely polluted sites in East Asia, the decreased δ15N in wood also reflected the consistent deposition of 15N-depleted NHy. Though our data analysis represents only a subset of global forest sites where atmospheric N deposition is of interest, the results suggest that the direction and magnitude of the changes in the δ15N of forest samples are related to both atmospheric N and site conditions particularly for tropical vs. subtropical forests. Site-specific information on the atmospheric N deposition characteristics would allow more accurate assessment of the variations in the δ15N of forest samples in relation to N deposition.

Assessment of sources variability of riverine particulate organic matter with land use and rainfall changes using a three-indicator (δ13C, δ15N, and C/N) Bayesian mixing model.

In intensive agricultural watersheds, riverine particulate organic matter (POM) may be transported from many sources such as rice paddies, crop uplands, forests, and livestock farming areas during rainy seasons. However, the impacts of land-use and rainfall changes on the POM sources are not well understood. In this study, changes in the sources of riverine POM were investigated in an agricultural area of Korea between 2014 and 2020/21. During this period, land-use and rainfall patterns changed dramatically. The δ13C, δ15N, and C/N of the POM sources as well as those of riverine POM were analyzed, and a stable isotope analysis in R (SIAR) model was utilized for source apportionment. There were differences in δ13C, δ15N, and C/N among the sources. For example, manure had higher δ13C (-22.6 ± 3.3‰) and δ15N (+10.6 ± 5.9‰) than soils (from -28.0 ± 0.8‰ to -25.1 ± 1.2‰ for δ13C and +3.6 ± 1.7‰ to +9.8 ± 1.4‰ for δ15N). For soils, the δ13C and δ15N were higher for upland soils, while C/N was greater for forest soils than for others. For riverine POM, the δ15N marginally changed; however, the δ13C and C/N increased from -26.1 ± 0.9‰ to -20.8 ± 5.3‰ and from +7.7 ± 1.7 to +18.8 ± 8.3 between 2014 and 2020/21, respectively. The SIAR model showed that the contributions of paddy (from 41.0% to 14.9%) and upland fields (from 48.1% to 23.7%) to riverine POM decreased between the periods due to decreased paddy area and the implementation of best management practice on upland fields, respectively. However, the contribution of forests (from 3.5% to 28.0%) and manure (from 7.4% to 33.5%) increased probably due to improper management of forest clear-cutting sites and livestock manure storage sites. The contributions of agricultural soils to riverine POM decreased in drier years. Our study suggests that land management rather than land-use area is critical in riverine POM management, particularly in wetter years.

Pristine and engineered biochar for the removal of contaminants co-existing in several types of industrial wastewaters: A critical review.

Biochar has been widely studied as an adsorbent for the removal of contaminants from wastewater due to its unique characteristics, such as having a large surface area, well-distributed pores and high abundance of surface functional groups. Critical review of the literature was performed to understand the state of research in utilizing biochars for industrial wastewater remediation with emphasis on pollutants that co-exist in wastewater from several industrial activities, such as textile, pharmaceutical and mining industries. Such pollutants include organic (such as synthetic dyes, phenolic compounds) and inorganic contaminants (such as cadmium, lead). Multiple correspondence analyses suggest that through batch equilibrium, columns or constructed wetlands, researchers have used mechanistic modelling of isotherms, kinetics, and thermodynamics to evaluate contaminant removal in either synthetic or real industrial wastewaters. The removal of organic and inorganic contaminants in wastewater by biochar follows several mechanisms: precipitation, surface complexation, ion exchange, cation-π interaction, and electrostatic attraction. Biochar production and modifications promote good adsorption capacity for those pollutants because biochar properties stemming from production were linked to specific adsorption mechanisms, such as hydrophobic and electrostatic interactions. For instance, adsorption capacity of malachite green ranged from 30.2 to 4066.9 mg g-1 depending on feedstock type, pyrolysis temperature, and chemical modifications. Pyrolyzing biomass at above 500 °C might improve biochar quality to target co-existing pollutants. Treating biochars with acids can also improve pollutant removal, except that the contribution of precipitation is reduced for potentially toxic elements. Studies on artificial intelligence and machine learning are still in their infancy in wastewater remediation with biochars. Meanwhile, a framework for integrating artificial intelligence and machine learning into biochar wastewater remediation systems is proposed. The reutilization and disposal of spent biochar and the contaminant release from spent biochar are important areas that need to be further studied.

Biochar-induced reduction of N2O emission from East Asian soils under aerobic conditions: Review and data analysis.

Global meta-analyses showed that biochar application can reduce N2O emission. However, no relevant review study is available for East Asian countries which are responsible for 70% of gaseous N losses from croplands globally. This review analyzed data of the biochar-induced N2O mitigation affected by experimental conditions, including experimental types, biochar types and application rates, soil properties, and chemical forms and application rates of N fertilizer for East Asian countries. The magnitude of biochar-induced N2O mitigation was evaluated by calculating N2O reduction index (Rindex, percentage reduction of N2O by biochar relative to control). The Rindex was further standardized against biochar application rate by calculating Rindex per unit of biochar application rate (ton ha-1) (Unit Rindex). The Rindex averaged across different experimental types (n = 196) was -21.1 ± 2.4%. Incubation and pot experiments showed greater Rindex than column and field experiments due to higher biochar application rate and shorter experiment duration. Feedstock type and pyrolysis temperature also affected Rindex; either bamboo feedstock or pyrolysis at > 400 °C resulted in a greater Rindex. The magnitude of Rindex also increased with increasing biochar rate. Soil properties did not affect Rindex when evaluated across all experimental types, but there was an indication that biochar decreased N2O emission more at a lower soil moisture level in field experiments. The magnitude of Rindex increased with increasing N fertilizer rate up to 500-600 kg N ha-1, but it decreased thereafter. The Unit Rindex averaged across experimental types was -1.2 ± 0.9%, and it was rarely affected by experimental type and conditions but diminished with increasing biochar rate. Our results highlight that since N2O mitigation by biochar is affected by biochar application rate, Rindex needs to be carefully evaluated by standardizing against biochar application rate to suggest the best conditions for biochar usage in East Asia.

Biochar heavy metal removal in aqueous solution depends on feedstock type and pyrolysis purging gas.

The effectiveness of biochar as a sorptive material to remove contaminants, particularly heavy metals, from water is dependent on biomass type and pyrolysis condition. Biochars were produced from pulp mill sludge (PMS) and rice straw (RS) with nitrogen (N2) or carbon dioxide (CO2) as the purging gas. The sorptive capacity of the biochars for cadmium(II), copper(II), nickel(II) and lead(II) was studied. The heavy metal adsorption capacity was mainly affected by biomass type, with biochars adsorption capacities higher for lead(II) (109.9-256.4 mg g-1) than for nickel(II) (40.2-64.1 mg g-1), cadmium(II) (29.5-42.7 mg g-1) and copper(II) (18.5-39.4 mg g-1) based on the Langmuir adsorption model. The highest lead(II) adsorption capacities for PMS and RS biochars were 256.4 and 133.3 mg g-1, respectively, when generated using N2 as the purging gas. The corresponding lead(II) adsorption capacities were 250.0 and 109.9 mg g-1, respectively, when generated using CO2 as the purging gas. According to the intraparticle diffusion model, 30-62% of heavy metal adsorption was achieved in 1 h; film diffusion was the rate-dominating step, whereas pore diffusion was a rate-limiting step. Ion exchange and complexation between heavy metals and biochar surface functional groups such as carbonyl and hydroxyl groups were effective mechanisms for heavy metal sorption from the aqueous solution. We conclude that proper selection of both the feedstock type and the purging gas is important in designing biochars for the effective removal of potentially toxic metals from wastewater.

Rice straw cover decreases soil erosion and sediment-bound C, N, and P losses but increases dissolved organic C export from upland maize fields as evidenced by δ13C.

Soil surface with crop residue is effective in reducing soil erosion and carbon (C), nitrogen (N), and phosphorus (P) losses from sloping fields. However, there is a high possibility that surface cover increases export of dissolved organic C (DOC) though relevant field studies under natural rainfall are lacking. In this study, the effects of surface cover with rice (Oryza sativa L.) straw on soil and CNP losses in both dissolved and sediment-bound forms from maize (Zea mays L.) fields were investigated under two fertilization levels (standard and double) × two types of runoff experiments (natural rainfall and artificial irrigation). Changes in soil properties including moisture, temperature, nutrients, and C concentration as well as maize yield were also examined. Surface cover decreased soil and total CNP losses by up to 82% across the experimental plots with some exceptions. However, surface cover increased DOC export in both natural (by 68-82% in total across all events) and artificial (by 3-4 fold) runoff, suggesting that crop residue cover may act as a DOC pollution source of water bodies. The contribution of rice straw to DOC, which was calculated using the δ13C of DOC from covered plots (-24.1 to -28.0‰) and control plots (-19.6 to -25.1‰), was 52.5-95.8%. The concentrations of K2SO4-extractable and microbial biomass C of the soils did not differ between covered and control plots, suggesting that DOC produced from rice straw was not incorporated into the soils, but rather, was washed out with surface runoff in this study. Surface cover increased maize growth and yield, particularly in double fertilization plots, through improved soil moisture, temperature, and nutrient conditions. To take full advantage of surface cover with crop residue, a further study on reducing DOC loss from crop residue needs to be conducted.

Carboxyl and hydroxyl groups enhance ammonium adsorption capacity of iron (III) chloride and hydrochloric acid modified biochars.

The effectiveness of the modification of wheat straw biochar using FeCl3 and HCl, alone or combined, on ammonium adsorption was evaluated using kinetic and isotherm models. The adsorption mechanisms were studied by comparative analysis of the surface properties of the biochars before and after ammonium adsorption. The results indicate that the modification methods enhanced the ammonium adsorption capacity by at least 14%, due to the increased OH and OCO functional groups and specific surface area, and increased Fe3+/Fe2+ redox coupling serving as an electron shuttle. It can be concluded that chemical modification of wheat straw biochars using FeCl3 and HCl increased the effectiveness of biochars for the treatment of ammonium-contaminated wastewater.

Biochar surface complexation and Ni(II), Cu(II), and Cd(II) adsorption in aqueous solutions depend on feedstock type.

Biochar is a promising material for efficient removal of toxic metals from wastewater to meet standards for discharge into surface water. We characterized adsorption behaviour of willow (Salix alba) wood (WW) and cattle manure (CM) and their biochars, willow wood biochar (WWB) and cattle manure biochar (CMB), and elucidated the mechanisms for the removal of Ni(II), Cu(II) and Cd(II) from aqueous solutions. The kinetic adsorption suggests that the adsorption of Ni(II), Cu(II) and Cd(II) by feedstock and their biochars was controlled by mass transport, and chemisorption also played a role in the adsorption process. The Elovich model also well described the adsorption kinetics for WW and CM (R2 > 0.92), indicating that heterogeneous diffusion was the mechanism. The Sips isotherm model fitted best (R2 > 0.98) for Ni(II), Cu(II) and Cd(II) adsorption by the feedstocks and their biochars, indicating that both monolayer and multilayer adsorption played roles on the heterogeneous surfaces of the four adsorbents. The WWB had a higher while the CMB had a lower adsorption capacity than their respective feedstock due to the presence of abundant -COOH functional group on WWB surface to interact with Ni(II), Cu(II) and Cd(II) to form surface complexes. The higher specific surface area and lower pH of point of zero charge (PZC) of WWB were other contributing factors for its greater removal capacity. Therefore, we conclude that proper feedstocks need to be selected to produce biochars that are efficient for the removal of toxic metals from wastewater.

Fly ash and zeolite decrease metal uptake but do not improve rice growth in paddy soils contaminated with Cu and Zn.

Fly ash (FA) and zeolite (Z) are known to reduce bioavailability of metals in soils via immobilization; however, these amendments may not only immobilize metals such as copper (Cu) and zinc (Zn), but also reduce nitrogen (N) and phosphorus (P) availability in the soils via sorption (for N by Z) and precipitation (for P by FA). This study was conducted to evaluate the effects of application of FA and Z (0, 5, and 10% rate) on the availability of nutrients as well as metals in the metal-contaminated soils cultivated with paddy rice (Oryza sativa L.). Both FA and Z reduced Cu and Zn uptake by rice while increasing metal retention in the soils regardless of the application rates. However, reduced uptake of metals did not translate into increase in rice growth, especially at the 10% of amendment rates, due to decreased nutrient uptake as indicated by higher NH4+ and available P concentration in the soils amended with Z and FA, respectively, which inhibited tillering in the early rice growth period and thus reduced biomass accumulation at maturity. Our results suggest that FA and Z may reduce Cu and Zn uptake by rice in the soils contaminated with the metals; however, the availability of N and P is likely to be co-decreased. We suggest that the capacities of FA and Z to immobilize nutrients as well as metals need to be considered prior to using the amendments in metal-contaminated rice paddies.

Biochar properties and lead(II) adsorption capacity depend on feedstock type, pyrolysis temperature, and steam activation.

Biochar is a promising material for facilitating the reclamation of oil sands process water (OSPW); however, how biochar properties can be optimized for metal removal from OSPW is not well studied. This study was conducted to determine relationships among feedstock type, pyrolysis condition, biochar property, and lead(II) adsorption capacity to demonstrate the potential use of biochar for metal removal from a synthetic OSPW. Sawdust, canola and wheat straw, and manure pellet were pyrolyzed at 300, 500, and 700 °C, with or without steam activation. Increasing pyrolysis temperature increased, with a few exceptions, biochar pH, surface area, and carbon content, but decreased hydrogen and oxygen contents and surface functional groups. Steam activation increased surface area but did not affect other properties. For non-steam-activated biochars, canola and wheat straw biochars produced at 700 °C had the highest lead(II) adsorption capacity (Qmax_Pb), at 108 and 109 mg g-1, respectively. Increasing the pyrolysis temperature increased Qmax_Pb due to increased biochar pH, ash content, and surface area by increasing precipitation, ion exchange, and inner-sphere complexation of lead(II). Steam activation increased lead(II) adsorption capacity for most biochars mainly due to the increased surface area, with the highest Qmax_Pb at 195 mg g-1 for canola straw biochar pyrolyzed at 700 °C with steam activation. The adsorption with time followed a pseudo-second order kinetic model. The results of this study will help select most effective biochars that can be produced from locally available agricultural or forestry byproducts that are optimized for metal removal from synthetic OSPW.

Long-term N and S addition and changed litter chemistry do not affect trembling aspen leaf litter decomposition, elemental composition and enzyme activity in a boreal forest.

The effect of long-term nitrogen (N) and sulfur (S) deposition on litter mass loss and changes in carbon (C), N, and S composition and enzyme activities during litter decomposition was investigated in a boreal forest. This study included four N × S treatments: control (CK), N application (30 kg N ha-1 yr-1), S application (30 kg S ha-1 yr-1), and N plus S application (both at 30 kg ha-1 yr-1). Two experiments were conducted for 22 months: 1) a common litter decomposition experiment with litter bags containing a common litter (same litter chemistry) and 2) an in-situ litter decomposition experiment with litter from each treatment plot (and thus having different litter chemistry). Litterbags were placed onto the four treatment plots to investigate the direct effect of N and S addition and the combined effect of N and/or S addition and litter chemistry on litter decomposition, respectively. Regardless of the source of litter, N and/or S addition affected C, N and S composition at a certain period of the experiment but did not affect litter mass loss and enzyme activity throughout the experiment, indicating that the N and S addition rates were below the critical level required to affect C and N cycling in the studied ecosystem. However, the greater change in N composition per unit of litter mass loss in the N addition treatment than in the other treatments in the common litter but not in the in-situ litter experiment, suggests that the effect of N addition on N loss and retention depends on the initial litter chemistry. We conclude that the studied N and S addition rates did not affect litter decomposition and elemental cycling in the studied forest ecosystem even though the N and S addition rates were much greater than their ambient deposition rates.

Introducing trees to agricultural lands increases greenhouse gas emission during spring thaw in Canadian agroforestry systems.

The role of agroforestry systems in mitigating greenhouse gas (GHG) emission from agricultural soils during spring thaw (early April to mid-May) has been poorly studied. Soil CO2, CH4 and N2O fluxes were measured from treed areas and adjacent herblands (areas without trees) during spring thaw in 2014 and 2015 at 36 agroforestry sites (12 hedgerow, 12 shelterbelt and 12 silvopasture) in central Alberta, Canada. Fluxes of those GHGs varied with agroforestry systems and land-cover types. We found greater CO2 emission (P < 0.001) and CH4 uptake (P < 0.05), but lower N2O emission (P < 0.01) in the silvopasture than in the hedgerow and shelterbelt systems, with no difference between the last two systems. Treed areas in general had greater CO2 emissions (P < 0.001) and CH4 uptake (P < 0.01), and lower N2O emissions (P < 0.001) than the herblands. Soil temperature, moisture content, organic C content and soil available N concentration affected GHG fluxes. The global warming potential (GWP) was greater (P < 0.05) in the silvopasture than in the hedgerow or shelterbelt systems over the two spring thaw seasons examined, and greater (P < 0.05) in the treed areas than in the herblands during the cool spring in 2015. However, the GWP per unit soil organic C was lower in the treed areas (0.004-0.101%) than in the herblands (0.005-0.225%). As compared to previously reported mean growing season GHG emission (15.4 g CO2-eq m-2 day-1), the GWP of these land uses during spring thaw was small (<5% of the annual GWP) due to the short spring period (6 weeks) and the small GHG emission (2.5 g CO2-eq m-2 day-1). Although GHG emissions during spring thaw were small compared to those in the growing season, they should not be ignored.

Pine sawdust biochar reduces GHG emission by decreasing microbial and enzyme activities in forest and grassland soils in a laboratory experiment.

This study investigated the effects of biochar soil amendment on greenhouse gas (GHG) emissions in soils. Pine (Pinus koraiensis Siebold & Zucc.) sawdust biochar was produced at 300 and 550°C with and without steam activation (coded as BC300-S, BC550-S, BC300 and BC550, respectively). They were applied to forest and grassland soils at 1.5% (w/w) rate in a 100-day laboratory incubation experiment. Application of BC550 significantly reduced cumulative CO2 emission from the forest soil by 16.4% relative to the control (without biochar application), but not from the grassland soil. Biochar application did not have significant effects on CH4 uptake from either soil. Application of BC550 and BC550-S reduced the cumulative N2O emission by 27.5 and 31.5%, respectively, in the forest soil and 14.8 and 11.7%, respectively, in the grassland soil, as compared to the control. The effects of BC300 and BC300-S on cumulative CO2 and N2O emission was not significant in both soils, except for the significant reduction in cumulative N2O emission from the forest soil by BC300-S. The effect of BC550 and BC550-S on N2O emission persisted until the end of the 100-day incubation indicating possible long-term effects of these biochars. We conclude that BC550 and BC550-S had the highest potential to reduce CO2 and N2O emission in the 100-day laboratory incubation experiment. These biochars should be tested in long-term field trials to confirm their potential for mitigating CO2 and N2O fluxes in real ecosystems with a relevant time frame.

Coarse Woody Debris Increases Microbial Community Functional Diversity but not Enzyme Activities in Reclaimed Oil Sands Soils.

Forest floor mineral soil mix (FMM) and peat mineral soil mix (PMM) are cover soils commonly used for upland reclamation post open-pit oil sands mining in northern Alberta, Canada. Coarse woody debris (CWD) can be used to regulate soil temperature and water content, to increase organic matter content, and to create microsites for the establishment of microorganisms and vegetation in upland reclamation. We studied the effects of CWD on soil microbial community level physiological profile (CLPP) and soil enzyme activities in FMM and PMM in a reclaimed landscape in the oil sands. This experiment was conducted with a 2 (FMM vs PMM) × 2 (near CWD vs away from CWD) factorial design with 6 replications. The study plots were established with Populus tremuloides (trembling aspen) CWD placed on each plot between November 2007 and February 2008. Soil samples were collected within 5 cm from CWD and more than 100 cm away from CWD in July, August and September 2013 and 2014. Microbial biomass was greater (p<0.05) in FMM than in PMM, in July, and August 2013 and July 2014, and greater (p<0.05) near CWD than away from CWD in FMM in July and August samplings. Soil microbial CLPP differed between FMM and PMM (p<0.01) according to a principal component analysis and CWD changed microbial CLPP in FMM (p<0.05) but not in PMM. Coarse woody debris increased microbial community functional diversity (average well color development in Biolog Ecoplates) in both cover soils (p<0.05) in August and September 2014. Carbon degrading soil enzyme activities were greater in FMM than in PMM (p<0.05) regardless of distance from CWD but were not affected by CWD. Greater microbial biomass and enzyme activities in FMM than in PMM will increase organic matter decomposition and nutrient cycling, improving plant growth. Enhanced microbial community functional diversity by CWD application in upland reclamation has implications for accelerating upland reclamation after oil sands mining.

Changes in nitrogen isotopic compositions during composting of cattle feedlot manure: effects of bedding material type.

Temporal changes in delta(15)N of cattle feedlot manure during its composting with either rice hull (RHM) or sawdust (SDM) as bedding materials were investigated. Regardless of the bedding material used, the delta(15)N of total N in the manure increased sharply from +7.6 per thousand to +9.9 per thousand and from +11.4 per thousand to +14.3 per thousand, respectively, in RHM or SDM, within 10 days from the commencement of composting. Such increases could be attributed primarily to N loss via NH(3) volatilization and denitrification based on the very high delta(15)N values (greater than +20 per thousand) of NH(4)(+) and NO(3)(-) in the co-composted manure. The delta(15)N of total N in RHM was substantially lower (by more than 3 per thousand) than that in SDM, suggesting that the delta(15)N of the composted manure was affected not only by N loss but also by the type of bedding material used. Specifically, the higher N concentration in the rice hull than in the saw dust could lead to a greater (15)N isotope dilution.