Effects of organic material amendment and water content on NO, N2O, and N2 emissions in a nitrate-rich vegetable soil

Amending vegetable soils with organic materials is increasingly recommended as an agroecosystems management option to improve soil quality. However, the amounts of NO, N₂O, and N₂ emissions from vegetable soils treated with organic materials and frequent irrigation are not known. In laboratory-based experiments, soil from a NO ₃ ^? -rich (340 mg N?kg^?1) vegetable field was incubated at 30°C for 30 days, with and without 10 % C₂H₂, at 50, 70, or 90 % water-holding capacity (WHC) and was amended at 1.19 g?C kg^?1 (equivalent to 2.5 t?C ha^?1) as Chinese milk vetch (CMV), ryegrass (RG), or wheat straw (WS); a soil not amended with organic material was used as a control (CK). At 50 % WHC, cumulative N₂ production (398–524 μg N?kg^?1) was significantly higher than N₂O (84.6–190 μg N?kg^?1) and NO (196–224 μg N?kg^?1) production, suggesting the occurrence of denitrification under unsaturated conditions. Organic materials and soil water content significantly influenced NO emissions, but the effect was relatively weak since the cumulative NO production ranged from 124 to 261 μg N?kg^?1. At 50–90 % WHC, the added organic materials did not affect the accumulated NO ₃ ^? in vegetable soil but enhanced N₂O emissions, and the effect was greater by increasing soil water content. At 90 % WHC, N₂O production reached 13,645–45,224 μg N?kg^?1 from soil and could be ranked as RG?>?CMV?>?WS?>?CK. These results suggest the importance of preventing excess water in soil while simultaneously taking into account the quality of organic materials applied to vegetable soils.     

The bioaccumulation of Cd in rice grains in paddy soils as affected and predicted by soil properties

Purpose

The area of cadmium (Cd)-contaminated soil in China is increasing due to the rapid development of the Chinese economy. To ensure that the rice produced in China meets current food safety and quality standards, the current soil quality standards for paddy soils urgently need to be updated.

Materials and methods

We conducted a pot experiment with 19 representative paddy soils from different parts of China to study the effects of soil properties on bioaccumulation of Cd in rice grains. The experiment included a control, a low treatment concentration (0.3 mg kg^–1 for pH?<?6.5 and 0.6 mg kg^–1 for pH?≥?6.5), and a high treatment concentration (0.6 mg kg^–1 for pH?<?6.5 and 1.2 mg kg^–1 for pH?≥?6.5) of Cd salt added to soils.

Results and discussion

The results showed that the Cd content in grains of the control and low and high Cd treatments ranged from 0.021 to 0.14, 0.07 to 0.27, and 0.12 to 0.33 mg kg^–1, respectively. Stepwise multiple regression analysis indicated that soil pH and organic carbon (OC) content could explain over 60 % of the variance in the (log-transformed) bioaccumulation coefficient (BCF) of Cd in grains across soils. Aggregated boosted trees analysis showed that soil pH and OC were the main factors controlling Cd bioavailability in paddy soils. Validation of the models against data from recent literature indicated that they were able to accurately predict the BCF in paddy soils.

Conclusions

These quantitative relationships between the BCF of Cd in grains and soil properties are helpful for developing soil-specific guidance on Cd safety threshold value for paddy soils.     

Soil organic carbon stocks in Veracruz State (Mexico) estimated using the 1:250,000 soil database of INEGI: biophysical contributions

Purpose

In this study, we quantified soil organic carbon (SOC) stocks and analyzed their relationship with biophysical factors and soil properties.

Materials and methods

The study region was Veracruz State, located in the eastern part of Mexico, covering an area of 72,410 km². A soil database that contains physicochemical analyses of soil horizons such as carbon concentration data was the source of information used in this study. The database consisted of 163 soil profiles representing 464 genetic horizons. Statistical analysis was used to investigate the effect of each factor (climate, altitude, slope) on SOC stock to 0.50 m depth and to assess differences in the distribution of SOC stock in terms of soil depth (0.0–0.20, 0.20–0.40, 0.40–0.60, 0.60–0.80, 0.80–1.0 m) and land use. In order to compute the spatial distribution of SOC stock to 0.50 m depth based on the soil sampling location, the kriging method was used.

Results and discussion

Results indicated that SOC stock (0.50 m depth) ranged between 0.44 and 41.2 kg C m^?2. Regression analysis showed that SOC stocks (0.50 m depth) are negatively correlated with temperature (r?=??0.38; P?<?0.001) and positively correlated with altitude (r?=?0.40; P?<?0.001) and slope (r?=?0.40; P?<?0.001). In addition, by multiple regression, temperature combined with precipitation explained more SOC stock variations (r?=?0.43; P?<?0.001) than the regression model with precipitation (r?=?0.13; P?=?0.16) alone. Also, slope combined with temperature and precipitation explained more SOC stock variations (r?=?0.46; P?<?0.001) than the regression model with slope alone. Forest lands, grasslands, and croplands have higher SOC stocks in the 0.0–0.20-m soil layer than in deeper layers. On average, forest lands, grasslands, croplands, and other lands (wetland and dunes) had a SOC stock of 13.6, 14.6, 15.1, and 8.5 kg C m^?2 at 1 m depth, respectively. Soil color correlated (?0.25 ≤ r ≤ ?0.89) with SOC content.

Conclusions

Overall, these results indicate the influence of major interactions between biophysical factors and SOC stocks. This research indicated that SOC stock decreased with soil depth, but with slight variations depending on land use. Thus, there remains a need for more SOC data that include an improved distribution of soil sampling points in order to entirely understand the contributions of biophysical factors to SOC stocks in Veracruz State.     

The effect of concentrations and properties of phenanthrene, pyrene, and benzo(a)pyrene on desorption in contaminated soil aged for 1 year

Purpose

The choice and timing of microorganisms added to soils for bioremediation is affected by the dominant bioavailable contaminants in the soil. However, changes to the concentration of bioavailable PAHs in soil are not clear, especially when several PAHs coexist. This study investigated the effects of PAH concentration and chemical properties on desorption in meadow brown soil after a 1-year aging period, which could reflect changes of PAH bioavailability during bioremediation.

Materials and methods

Based on the percentage of different molecular weights in a field investigation, high-level contaminated soil (HCS) and low-level contaminated soil (LCS) were prepared by adding phenanthrene (PHE), pyrene (PYR) and benzo(a)pyrene (BaP) to uncontaminated meadow brown soil. The concentrations of HCS and LCS were 250 mg?kg^?1 (PHE, PYR, and BaP: 100, 100, and 50 mg?kg^?1) and 50 mg?kg^?1 (PHE, PYR, and BaP: 20, 20, and 10 mg?kg^?1) respectively. The soils were aged for 1 year, after which desorption was induced by means of a XAD-2 adsorption technique over a 96-h period.

Results and discussion

The range of the rapidly desorbing fraction (F _rap) for PHE, PYR, and BaP in HCS and LCS was from 1.9 to 27.8 %. In HCS, desorption of PYR was most difficult, and the rate constant of very slow desorption (K _vs) of PYR was 8 orders of magnitude lower than that of BaP, which had similar very slow desorbing fractions (49.8 and 50.5 %, respectively). However, in LCS, desorption of PYR was the easiest; the K_vs of PYR was 8–10 orders of magnitude higher than those of PHE and BaP. In HCS, the time scale for release of 50 % of the PAHs was ranked as BaP?>?PYR?>?PHE, while in LCS this was BaP?>?PHE?>?PYR.

Conclusions

The combined effect of PAH concentrations and properties should be taken into account during desorption. The desorption of PAH did not always decrease with increasing molecular weight, and the desorption of four-ring PAHs might be special. These results are useful for screening biodegrading microbes and determining when they should be added to soils based on the dominant contaminants present during different periods, thus improving the efficiency of soil bioremediation.     

Organic carbon mineralization responses to temperature increases in subtropical paddy soils

Purpose

Understanding organic carbon mineralization and its temperature response in subtropical paddy soils is important for the regional carbon balance. There is a growing interest in factors controlling soil organic carbon (SOC) mineralization because of the potential for climate change. This study aims to test the hypothesis that soil clay content impedes SOC mineralization in subtropical paddy soils.

Materials and methods

A 160-day laboratory incubation at temperatures from 10 to 30 °C and 90% water content was conducted to examine the dynamics of SOC mineralization and its temperature response in three subtropical paddy soils with different clay contents (sandy loam, clay loam, and silty clay soils). A three-pool SOC model (active, slow, and resistant) was used to fit SOC mineralization.

Results and discussion

Total CO₂ evolved during incubation following the order of clay loam > silty clay > sandy loam. The temperature response coefficients (Q ₁₀) were 1.92?±?0.39, 2.36?±?0.22, and 2.10?±?0.70, respectively, for the sandy loam soil, clay loam soil, and silty clay soil. But the soil clay content followed the order of silty clay > clay loam > sandy loam. The sandy loam soil neither released larger amounts of CO₂ nor showed higher temperature sensitivity, as expected, even though it contains lower soil clay content among the three soils. It seems that soil clay content did not have a dominant effect which results in the difference in SOC mineralization and its temperature response in the selected three paddy soils. However, dissolved organic carbon (DOC; representing substrate availability) had a great effect. The size of the active C pool ranged from 0.11 to 3.55% of initial SOC, and it increased with increasing temperature. The silty clay soil had the smallest active C pool (1.40%) and the largest Q ₁₀ value (6.33) in the active C pool as compared with the other two soils. The mineralizable SOC protected in the silty clay soil, therefore, had even greater temperature sensitivity than the other two soils that had less SOC stabilization.

Conclusions

Our study suggests that SOC mineralization and its temperature response in subtropical paddy soils were probably not dominantly controlled by soil clay content, but the substrate availability (represented as DOC) and the specific stabilization mechanisms of SOC may have great effects.     

Immobilization of Cu and Cd in a contaminated soil: one- and four-year field effects

Purpose

Many amendments have been applied to immobilize heavy metals in soil. However, little information is available on the changes of immobilization efficiencies of heavy metals in contaminated soils over time. This work investigated the immobilization efficiencies of copper (Cu) and cadmium (Cd) in contaminated soils in situ remediated with one-time application of three amendments for 1 year and 4 years.

Materials and methods

Apatite, lime, and charcoal were mixed with the topsoil of each plot with the amounts of 22.3, 4.45, and 66.8 t/ha, respectively. Soil chemical properties and fractions of Cu and Cd were examined after in situ remediation for 1 year and 4 years. Soil sorption and retention capacities and desorption proportions for Cu and Cd were investigated by batch experiments.

Results and discussion

The addition of amendments significantly increased soil pH, but decreased exchange acid and aluminum (Al). The amendments significantly decreased the CaCl₂ extractable Cu and Cd and transformed them from active to inactive fractions. After the application of amendments for 1 year, the maximum sorption capacities ranged from 35.6 to 38.8 mmol/kg for Cu and from 14.4 to 17.0 mmol/kg for Cd, which were markedly higher than those of the application of amendments for 4 years (Cu, 29.6–34.7 mmol/kg; Cd, 10.9–16.4 mmol/kg). Desorption proportions (D) of Cu and Cd using three extractants followed the order of \( {D}_{{\mathrm{NaNO}}_3}<{D}_{{\mathrm{CaCI}}_2}<{D}_{{\mathrm{MgCI}}_2} \) . Moreover, the retention capacities (R) of Cu and Cd both increased and followed the order of R _apatite?>?R _lime?>?R _charcoal, resulting in higher Cu and Cd in the amended soils than the untreated soil.

Conclusions

Apatite, lime, and charcoal increased the soil sorption and retention capacities of Cu and Cd and resulted in higher immobilization efficiencies in the amended soils than the untreated soil. However, the immobilization efficiencies of Cu and Cd decreased with the decrease of sorption capacities after 4 years. It was concluded that apatite had the best effect on the long-term stability of immobilized Cu and Cd and can be applied to immobilize heavy metals in contaminated soils.     

Effect of 7-year application of a nitrification inhibitor, dicyandiamide (DCD), on soil microbial biomass, protease and deaminase activities, and the abundance of bacteria and archaea in pasture soils

Purpose

The nitrification inhibitor dicyandiamide (DCD) has been shown to be highly effective in reducing nitrate (NO₃ ^?) leaching and nitrous oxide (N₂O) emissions when used to treat grazed pasture soils. However, there have been few studies on the possible effects of long-term DCD use on other soil enzyme activities or the abundance of the general soil microbial communities. The objective of this study was to determine possible effects of long-term DCD use on key soil enzyme activities involved in the nitrogen (N) cycle and the abundance of bacteria and archaea in grazed pasture soils.

Materials and methods

Three field sites used for this study had been treated with DCD for 7 years in field plot experiments. The three pasture soils from three different regions across New Zealand were Pukemutu silt loam in Southland in the southern South Island, Horotiu silt loam in the Waikato in the central North Island and Templeton silt loam in Canterbury in the central South Island. Control and DCD-treated plots were sampled to analyse soil pH, microbial biomass C and N, protease and deaminase activity, and the abundance of bacteria and archaea.

Results and discussion

The three soils varied significantly in the microbial biomass C (858 to 542 μg C g^?1 soil) and biomass N (63 to 28 μg N g^?1), protease (361 to 694 μg tyrosine g^?1 soil h^?1) and deaminase (4.3 to 5.6 μg NH₄ ⁺ g^?1 soil h^?1) activity, and bacteria (bacterial 16S rRNA gene copy number: 1.64?×?10⁹ to 2.77?×?10⁹ g^?1 soil) and archaea (archaeal 16S rRNA gene copy number: 2.67?×?10⁷ to 3.01?×?10⁸ g^?1 soil) abundance. However, 7 years of DCD use did not significantly affect these microbial population abundance and enzymatic activities. Soil pH values were also not significantly affected by the long-term DCD use.

Conclusions

These results support the hypothesis that DCD is a specific enzyme inhibitor for ammonia oxidation and does not affect other non-target microbial and enzyme activities. The DCD nitrification inhibitor technology, therefore, appears to be an effective mitigation technology for nitrate leaching and nitrous oxide emissions in grazed pasture soils with no adverse impacts on the abundance of bacteria and archaea and key enzyme activities.     

Impact of organic matter addition on pH change of paddy soils

Purpose

The objective of the present study was to explore the effect of initial pH on the decomposition rate of plant residues and the effect of residue type on soil pH change in three different paddy soils.

Materials and methods

Two variable charge paddy soils (Psammaquent soil and Plinthudult soil) and one constant charge paddy soil (Paleudalfs soil) were used to be incubated at 45 % of field capacity for 105 days at 25 °C in the dark after three plant residues (Chinese milk vetch, wheat straw, and rice straw) were separately added at a level of 12 g?kg^?1 soil. Soil pH, CO₂ escaped, DOC, DON, MBC, MBN, NH ₄ ⁺ , and NO ₃ ^? during the incubation period were dynamically determined.

Results and discussion

Addition of the residues increased soil pH by 0.1–0.8 U, and pH reached a maximum in the Psammaquent and Plinthudult soils with low initial pH at day 105 but at day 3 in the Paleudalfs soil with high initial pH. Incorporation of Chinese milk vetch which had higher concentration of alkalinity (excess cations) and nitrogen increased soil pH more as compared with incorporation of rice and wheat straws. Microbial activity was the highest in Chinese milk vetch treatment, which resulted in the highest increase of soil pH as compared with addition of rice and wheat straws. However, nitrification seemed to be inhibited in the variable charge soils of Psammaquent and Plinthudult but not in the constant charge soil of Paleudalfs.

Conclusions

The effectiveness of increasing soil pH after incorporation of the plant materials would be longer in low initial pH soils of Psammaquent and Plinthudult than in high initial pH soil of Paleudalfs. In order to achieve the same degree of pH improvement, higher amounts of plant residues should be applied in constant charge soils than in variable charge soils.     

Effects of soil pH and salt on N2O production in adjacent forest and grassland soils in central Alberta, Canada

Purpose

The effects of soil pH manipulation and KCl addition on N₂O production in adjacent forest and grassland soils in central Alberta were studied in a 16-day laboratory incubation experiment.

Materials and methods

The soils were subjected to four pH and two salt treatments: CK (control)—no addition of acid or alkali solution (pH 4.50 and 4.48 for the forest and grassland soils, respectively; same below); HCl—addition of HCl solution to lower soil pH (3.95 and 3.75); L-KOH and H-KOH—addition of 6 mL of 0.2 (5.36 and 5.57) and 0.4 (6.41 and 6.72)?mol?L^?1 KOH solution, respectively, to increase soil pH to two different levels. In order to differentiate between the effect of a change in pH and of changed salt concentrations on N₂O production, 6 mL of 0.2 (L-KCl) (4.56 and 4.41) or 0.4 mol?L^?1 (H-KCl) (4.59 and 4.42) KCl solutions were also applied as treatments to create two levels of salt application rates.

Results and discussion

Increasing pH promoted gross nitrification and cumulative N₂O production in both soils, particularly in the forest soil. However, cumulative N₂O production decreased in the forest soil but increased in the grassland soil when pH decreased. Cumulative N₂O production in the grassland soil was 36 times higher in the L-KCl treatment (1,442 μg?N?kg^?1) than in the CK (40 μg?N?kg^?1), whereas the H-KCl treatment reduced cumulative N₂O production. In contrast, in the forest soil, both KCl treatments reduced cumulative N₂O production.

Conclusions

(1) The most important factor to increase N₂O production in this study was increasing soil pH, suggesting that careful soil pH management could be used as a tool to control soil N₂O production; (2) salt effect was also involved in affecting N₂O production.     

Exploring the effect of organic matter on the interactions between mineral particles and cations with Wien effect measurements

Purpose

Understanding of the interactions between cations, mineral particles, and organic matter (OM) in soils is of paramount importance in plant nutrition and environmental science, and thus, these phenomena have been studied extensively. At present, an effective and simple tool to investigate these interactions does not exist. Based on previous studies of Wien effect in suspensions, the interactions of cations with soil mineral particles, complicated by the presence of organic matter, can be easily determined by means of Wien effect measurements, which was the objective of this study.

Materials and methods

A paddy soil originating from a yellow-brown soil, rich in organic matter, served as a test sample, from which the clay fraction of less than 2 μm in diameter was separated. Organic matter of aliquots of the clay fraction was removed by the oxidation with hot H₂O₂, and the natural and OM-free samples were saturated with various cations: Na⁺, K⁺, Ca²⁺, and Cd²⁺. The effects of OM present in the paddy soil on the interactions between the cations and the soil mineral particles were investigated by measuring the suspension Wien effect with a homemade apparatus, SHP-2.

Results and discussion

The weak electrical field electrical conductivities (EC₀) of suspensions of the natural soils saturated with various cations were higher than those of the OM-free soils. The rate of increase in electrical conductivity of suspensions of the OM-free soil, except that of suspensions saturated with Na⁺, at electrical field strengths >50～100 kV?cm^?1 was higher than those of the natural soil suspensions. The presence of OM increased the mean free binding energies of cations other than Na⁺. The increasing binding energies for K⁺ and Ca²⁺ were 0.56 and 0.57 kJ?mol^?1, respectively, which were significantly larger than the increase for Cd²⁺ as only 0.03 kJ?mol^?1. The binding energies of various cations on both natural and OM-free soils were all in the order: Na⁺?<?K⁺?<?Ca²⁺≈Cd²⁺. As opposed to its effect on the binding energies, the presence of OM reduced the mean free adsorption energies of the cations. Except for Na⁺, the adsorption energies of K⁺, Ca²⁺, and Cd²⁺ at field strengths >50 kV?cm^?1 were lower in the natural soil as compared with the OM-free soil, and the differences between the adsorption energies became larger with increasing field strengths. The presence of OM made the zeta potential of the soil particles saturated with Na⁺ and K⁺ positive, and the particles saturated with Ca²⁺ and Cd²⁺ negative.

Conclusions

Organic matter affected the interactions of cations with soil mineral particles significantly. Binding and adsorption energies, which were quantitative measures of the interactions between cations and soil particles, could be determined by Wien effect measurements in suspensions. The binding energies on natural soils were larger than those on the corresponding OM-free soils, and the adsorption energies on the natural soils were lower than those on OM-free soils.     

Is CO2 evolution in saline soils affected by an osmotic effect and calcium carbonate?

Salt-affected soils are widespread, particularly in arid climates, but information on nutrient dynamics and carbon dioxide (CO₂) efflux from salt-affected soils is scarce. Four laboratory incubation experiments were conducted with three soils. To determine the influence of calcium carbonate (CaCO₃) on respiration in saline and non-saline soils, a loamy sand (6.3% clay) was left unamended or amended with NaCl to obtain an electrical conductivity (EC) of 1.0 dS?m^?1 in a 1:5 soil/water extract. Powdered CaCO₃ at rates of 0%, 0.5%, 1.0%, 2.5%, 5.0% and 10.0% (w/w) and 0.25-2 mm mature wheat residue at 0% and 2% (w/w) were then added. Cumulative CO₂-C emission from the salt amended and unamended soils was not affected by CaCO₃ addition. To investigate the effect of EC on microbial activity, soil respiration was measured after amending a sandy loam (18.8% clay) and a silt loam (22.5% clay) with varying amount of NaCl to obtain an EC_1:5 of 1.0–8.0 dS?m^?1 and 2.5 g glucose C?kg^?1 soil. Soil respiration was reduced by more than 50% at EC_1:5?≥?5.0 dS?m^?1. In a further experiment, salinity up to an EC_1:5 of 5.0 dS?m^?1 was developed in the silt loam with NaCl or CaCl₂. No differences in respiration at a given EC were obtained between the two salts, indicating that Na and Ca did not differ in toxicity to microbial activity. The effect of different addition rates (0.25–2.0%) of mature wheat residue on the response of respiration to salinity was investigated by adding NaCl to the silt loam to obtain an EC_1:5 of 2.0 and 4.0 dS?m^?1. The clearest difference between salinity levels was with 2% residue rate. At a given salinity level, the modelled decomposition constant ‘k’ increased with increasing residue addition rate up to 1% and then remained constant. Particulate organic carbon left after decomposition from the added wheat residues was negatively correlated with cumulative respiration but positively correlated with EC. Inorganic N (NH ₄ ⁺ -N and NO ₃ ^? -N) and resin P significantly decreased with increasing salinity. Resin P was significantly decreased by addition of CaCl₂ and CaCO₃.     

Quantifying effects of primary parameters on adsorption–desorption of atrazine in soils

Purpose

Adsorption and desorption are important processes that influence the transport, transformation, and bioavailability of atrazine in soils. Equilibrium batch experiments were carried out to investigate the adsorption–desorption characteristics of atrazine. The objectives of this study were to (1) determine and quantify the main soil parameters governing atrazine adsorption and desorption phenomena; (2) find the correlativity between the identified soil parameters; and (3) investigate the universal desorption hysteresis traits.

Materials and methods

Fifteen soils with contrasting physico-chemical characteristics were collected from 11 provinces in eastern China. The equilibrium time was 24 h both for adsorption and desorption experiments. Atrazine was detected by Waters 2695/UV HPLC.

Results and discussion

Adsorption isotherms of atrazine could be well described by the Freundlich equation (r?≥?0.994, p?<?0.01). The total organic carbon (TOC) was the first independent variable that described 53.0 % of the total variability of K _f, followed by the pH (9.9 %), and the clay (4.0 %) and silt (1.2 %) contents, separately; while the primary soil properties that affect desorption parameters included the TOC, pH, free Fe₂O₃ (Fe_d) and the sand content, with the biggest contribution achieved by the TOC (ranged from 48.5–78.1 %). The results showed that when the content ratio of clay to TOC (RCO) was less than 40, the atrazine adsorption was largely influenced by the organic matrix, while when the RCO was greater than 40, they were vital affected by the clay content.

Conclusions

Adsorption–desorption isotherms of atrazine in soils were nonlinear. The content of TOC, clay, and iron oxides, as well as the pH value were the key soil parameters affecting the adsorption–desorption of atrazine in soil, among which the RCO especially exhibited relevance. Additionally, the desorption hysteresis existed for atrazine retention in all 15 tested soils, and the hysteretic effect enhanced with the increasing time for desorption. This would be ascribed to the heterogeneity physical–chemical properties of these soils.     

Mercury volatilization from a floodplain soil during a simulated flooding event

Purpose

Middle-European floodplain soils are often contaminated with mercury (Hg) and periodically flooded. In this study, the influence of a flooding event and subsequent dewatering on the volatilization of elemental Hg and methylated species was investigated in a laboratory experiment.

Material and methods

Undisturbed soil cores were taken from a topsoil (12.1?±?0.75 mg kg^?1 Hg) at the Elbe River in Lower Saxony, Germany. Soil columns were incubated at 20 °C with varying soil moisture (water-saturated for 2 weeks, 95 and 90 % water content for 1 week each), and the redox potential (E_H) was recorded. The gaseous Hg that accumulated in the headspace of the flux chamber of the columns was pumped over cooled traps filled with adsorber material and analyzed by gas chromatography/inductively coupled plasma mass spectrometry for the various Hg species.

Results and discussion

The watering of the soil resulted in a rapid decrease in the E_H and the achievement of strongly reducing conditions (E_H??1 Hg at the beginning to 5.78 μg L^?1 Hg at the end of the experiment. Species analyses revealed that exclusively elemental Hg volatilized. The volatilization rate was between 1.73 and 824 ng m^?2 h^?1 Hg, which is consistent with other studies at the Elbe River.

Conclusions

Even when flooded for a longer period of time, floodplain soils should show neither emission of methylated Hg nor exceptionally high volatilization of elemental Hg.     

Sediment denitrification in waterways in a rice-paddy-dominated watershed in eastern China

Purpose

Rice-paddy-dominated watersheds in eastern China are intensively cultivated, and lands with two crops receive as much as 550–600 kg?ha^–1?year^–1 of nitrogen (N), mainly through the addition of N-based fertilizers. However, stream N concentrations have been found to be relatively low. Waterways in the watersheds are assumed to be effective “sinks” for N, minimizing its downstream movement. We directly measured net sediment denitrification rates in three types of waterways (ponds, streams/rivers, and a reservoir) and determined the key factors that control net sediment denitrification. Such information is essential for evaluating the impact of the agricultural N cycle on the quality of surface water.

Materials and methods

The pond–stream–reservoir continuum was sampled every 2 months at nine sites in an agricultural watershed between November 2010 and December 2011. Net sediment N₂ fluxes/net sediment denitrification rates were determined by membrane inlet mass spectrometry and the N₂/Ar technique. A suite of parameters known to influence denitrification were also measured.

Results and discussion

Net denitrification rates ranged between 28.2?±?18.2 and 674.3?±?314.5 μmol N₂–N?m^–2?h^–1 for the streams, 23.7?±?23.9 and 121.2?±?38.7 μmol N₂–N?m^–2?h^–1 for the ponds, and 41.8?±?17.7 and 239.3?±?49.8 μmol N₂–N?m^–2?h^–1 for the reservoir. The mean net denitrification rate of the stream sites (173.2?±?248.4 μmol N₂–N?m^–2?h^–1) was significantly higher (p?<?0.001) than that of the pond sites (48.3?±?44.5 μmol N₂–N?m^–2?h^–1), and the three types of waterways all had significantly higher (p?<?0.01) mean net denitrification rates in summer than in other seasons. Linear regression and linear mixed effect model analysis showed that nitrate (NO₃ ^?–N) concentration in surface water was the primary controlling factor for net sediment denitrification, followed by water temperature. Using monitoring data on NO₃ ^?–N concentrations and temperature of the surface water of waterways and an established linear mixed effect model, total N removed through net sediment denitrification in the pond–stream–reservoir continuum was estimated at 46.8?±?24.0 t?year^–1 from July 2007 to June 2009, which was comparable with earlier estimates based on the mass balance method (34.3?±?12.7 t?year^–1), and accounted for 83.4 % of the total aquatic N. However, the total aquatic N was only 4.4 % of the total N input to the watershed, and thus most of the surplus N in the watershed was likely to be either denitrified or stored in soil.

Conclusions

High doses of N in a rice-paddy-dominated watershed did not lead to high stream N concentrations due to limited input of N into waterways and the high efficiency of waterways in removing N through denitrification.     

Pilot-scale counter-current acid leaching process for Cu,Pb, Sb,and Zn from small-arms shooting range soil

Purpose

The main objective of this study was to evaluate the potential of a counter-current leaching process (CCLP) on 14 cycles with leachate treatment at the pilot scale for Pb, Cu, Sb, and Zn removal from the soil of a Canadian small-arms shooting range.

Materials and methods

The metal concentrations in the contaminated soil were 904?±?112 mg Cu kg^–1, 8,550?±?940 mg Pb kg^–1, 370?±?26 mg Sb kg^–1, and 169?±?14 mg Zn kg^–1. The CCLP includes three acid leaching steps (0.125 M H₂SO₄?+?4 M NaCl, pulp density (PD)?=?10 %, t?=?1 h, T?=?20 °C, total volume?=?20 L). The leachate treatment was performed using metal precipitation with a 5-M NaOH solution. The treated effluent was reused for the next metal leaching steps.

Results and discussion

The average metal removal yields were 80.9?±?2.3 % of Cu, 94.5?±?0.7 % of Pb, 51.1?±?4.8 % of Sb, and 43.9?±?3.9 % of Zn. Compared to a conventional leaching process, the CCLP allows a significant economy of water (24,500 L water per ton of soil), sulfuric acid (133 L H₂SO₄ t^–1), NaCl (6,310 kg NaCl t^–1), and NaOH (225 kg NaOH t^–1). This corresponds to 82 %, 65 %, 90 %, and 75 % of reduction, respectively. The Toxicity Characteristic Leaching Procedure test, which was applied on the remediated soil, demonstrated a large decrease of the lead availability (0.8 mg Pb L^–1) in comparison to the untreated soil (142 mg Pb L^–1). The estimated total cost of this soil remediation process is 267 US$ t^–1.

Conclusions

The CCLP process allows high removal yields for Pb and Cu and a significant reduction in water and chemical consumption. Further work should examine the extraction of Sb from small-arms shooting range.     

Nitrification,acidification, and nitrogen leaching from subtropical cropland soils as affected by rice straw-based biochar: laboratory incubation and column leaching studies

Purpose

Few studies have examined the effects of biochar on nitrification of ammonium-based fertilizer in acidic arable soils, which contributes to NO₃ ^? leaching and soil acidification.

Materials and methods

We conducted a 42-day aerobic incubation and a 119-day weekly leaching experiment to investigate nitrification, N leaching, and soil acidification in two subtropical soils to which 300 mg N kg^?1 ammonium sulfate or urea and 1 or 5 wt% rice straw biochar were applied.

Results and discussion

During aerobic incubation, NO₃ ^? accumulation was enhanced by applying biochar in increasing amounts from 1 to 5 wt%. As a result, pH decreased in the two soils from the original levels. Under leaching conditions, biochar did not increase NO₃ ^?, but 5 wt% biochar addition did reduce N leaching compared to that in soils treated with only N. Consistently, lower amounts of added N were recovered from the incubation (KCl-extractable N) and leaching (leaching plus KCl-extractable N) experiments following 5 wt% biochar application compared to soils treated with only N.

Conclusions

Incorporating biochar into acidic arable soils accelerates nitrification and thus weakens the liming effects of biochar. The enhanced nitrification does not necessarily increase NO₃ ^? leaching. Rather, biochar reduces overall N leaching due to both improved N adsorption and increased unaccounted-for N (immobilization and possible gaseous losses). Further studies are necessary to assess the effects of biochar (when used as an addition to soil) on N.     

Remediation of organochlorine pesticides (OCPs) contaminated soil by successive hydroxypropyl-β-cyclodextrin and peanut oil enhanced soil washing–nutrient addition: a laboratory evaluation

Purpose

Problems associated with organochlorine pesticides (OCPs)-contaminated sites have received wide attention. To address the associated environmental concerns, innovative ex situ techniques are urgently needed.

Materials and methods

As regards long-term contamination by OCPs in Wujiang region, China, we investigated the feasibility of a cleanup strategy that employed hydroxypropyl-β-cyclodextrin (HPCD) and peanut oil to enhance ex situ soil washing for extracting OCPs, followed by the addition of supplemental nutrients to the residual soil.

Results and discussion

Elevated temperature (50 °C) in combination with ultrasonication (35 kHz, 30 min) at 50 g?L^?1 HPCD and 10 % peanut oil were effective in extracting, and therefore washing, the OCPs in soil. Ninety-three percent of total OCPs, 98 % of dichlorodiphenyltrichloroethanes, 93 % of chlordane as well as 85 % of Mirex were removed from soil after three successive washing cycles. Treating the residual soil with nutrients addition for 12 weeks led to significant increases (p?<?0.05) in the average well color development obtained by the BIOLOG Eco plate assay, Shannon–Weaver index, Simpson index, and EC₅₀ ecotoxicological evaluation compared with the controls. This implied that this cleanup strategy at least partially restored the microbiological functioning of the OCPs-contaminated soil and has the advantage of being an environmental-friendly technology.

Conclusions

The ex situ cleanup strategy through HPCD and peanut oil enhanced soil washing followed by nutrients addition could be effective in remediation of OCPs-contaminated soil.     

pH change, carbon and nitrogen mineralization in paddy soils as affected by Chinese milk vetch addition and soil water regime

Purpose

The aim of the research was to explore the effect of Chinese milk vetch (CM vetch) addition and different water management practices on soil pH change, C and N mineralization in acid paddy soils.

Materials and methods

Psammaquent and Plinthudult paddy soils amended with Chinese milk vetch at a rate of 12 g?kg^?1 soil were incubated at 25 °C under three different water treatments (45 % field capacity, CW; alternating 1-week wetting and 2-week drying cycles, drying rewetting (DRW) and waterlogging (WL). Soil pH, dissolved organic carbon, dissolved organic nitrogen (DON), CO₂ escaped, microbial biomass carbon, ammonium (NH₄ ⁺) and nitrate (NO₃ ^?) during the incubation period were dynamically determined.

Results and discussion

The addition of CM vetch increased soil microbial biomass concentrations in all treatments. The CM vetch addition also enhanced dissolved organic N concentrations in all treatments. The NO₃–N concentrations were lower than NH₄–N concentrations in DRW and WL. The pH increase after CM vetch addition was 0.2 units greater during WL than DRW, and greater in the low pH Plinthudult (4.59) than higher pH Paleudalfs (6.11) soil. Nitrogen mineralization was higher in the DRW than WL treatment, and frequent DRW cycles favored N mineralization in the Plinthudult soil.

Conclusions

The addition of CM vetch increased soil pH, both under waterlogging and alternating wet–dry conditions. Waterlogging decreased C mineralization in both soils amended with CM vetch. Nitrogen mineralization increased in the soils subjected to DRW, which was associated with the higher DON concentrations in DRW than in WL in the acid soil. Frequent drying–wetting cycles increase N mineralization in acid paddy soils.     

Study of the antimony species distribution in industrially contaminated soils

Purpose

The purpose of the present study was to investigate the distribution of antimony (Sb) and its species in soil fractions in order to understand better the real risk associated with Sb in the environment.

Materials and methods

Nine surface soil samples contaminated from lead/zinc and iron smelting operations and coal fired power plants were examined using: (1) four-step sequential extraction procedure (BCR); (2) two-step sequential extraction including ethylenediaminetetraacetic acid (EDTA), sodium hydroxide (NaOH) and NH₄F; and (3) single extraction with EDTA and NaOH. Liquid phase extraction was used for redox speciation of Sb. The distribution of Sb between soil fulvic and humic acids was determined after their chemical separation. The concentrations of Sb were measured by electrothermal atomic absorption spectrometry.

Results and discussion

The main part of total Sb (2.5–105 mg?kg^?1) was associated with the residual fraction in all soils. The exchangeable/carbonate-bound concentrations were 0.83–4.7 % of total Sb. Up to 6.8 % was in the reducible and up to 1.4 % was in the oxidizable fraction. EDTA removed 7.2–11.4 % of total content. Sb(V) was the predominant form in acetic acid and EDTA extracts. Single extraction with 0.1 mol?l^?1 NaOH released up to 13.7 % of soil antimony. The main part of Sb was complexed to the higher molecular weight fraction of soil-derived humic substances.

Conclusions

For highly contaminated soils, 4 % solubility in acetic acid could represent risk of contamination of ground water under specific conditions. Also, the relatively high phytoavailable Sb (7–11 %) can represent a significant proportion in highly polluted soils. Pentavalent antimony was the main antimony species extracted from soils. The main part of the organically antimony was found to be present as complexes with higher molecular weight humic acids fraction.     

Iron oxides serve as natural anti-acidification agents in highly weathered soils

Purpose

The effect of Fe oxides on the natural acidification of highly weathered soils was investigated to explore the natural acidification process in variable charge soils

Materials and methods

A variety of highly weathered soils with different Fe oxide contents were collected from the tropical and subtropical regions of southern China to investigate the soil acidity status. Electrodialysis experiments were conducted to simulate natural acidification process and promote accelerated acidification in a variety of systems such as relatively less weathered soils, mixtures of goethite with montmorillonite or kaolinite, an Alfisol, a limed Ultisol, and Fe oxides coated montmorillonite. The objective was to gather evidence for the occurrence of Fe oxide inhibited natural acidification in highly weathered soils.

Results and discussion

Highly weathered soils with free Fe₂O₃?<?100?g/kg (17 soils) had an average pH?=?4.64?±?0.06, while the soils with free Fe₂O₃?>?100?g/kg (49 soils) had an average pH?=?5.25?±?0.04. A significant linear relationship was found between the soil pH and Fe oxide content of these soils. Similar results were obtained in electrodialysis experiments, i.e., in soils that underwent accelerated acidification. A negative correlation was found between the Fe oxide content and exchangeable acidity or effective cation exchange capacity, respectively. In another set of experiments, goethite slowed down acidification in experiments conducted with this Fe oxide and montmorillonite, or kaolinite, or an Alfisol, or a limed Ultisol. The overlapping of the electrical double layers on the positively charged Fe oxide particles and negatively charged minerals may have caused the release and subsequent leaching of the base cations, but inhibited the production of exchangeable acidity cations. In addition, when montmorillonite or Fe oxide-coated montmorillonite were electrodialyzed in another set of experiments, exchangeable acidity of the former was much greater than that of the latter, suggesting that the positively charged Fe oxide coatings on montmorillonite have partially neutralized the permanent negative charge on montmorillonite surfaces, decreasing exchangeable acidity.

Conclusions

Fe oxides may function as natural ??anti-acidification?? agents through electric double-layer overlapping and coating of phylliosilicates in highly weathered soils.