A Greener UV and Peroxide-Based Chemical Oxygen Demand Test

Water quality assessment typically includes the determination of chemical oxygen demand (COD) by oxidation of organic matter with Cr(VI) in an acidic medium followed by digestion. Unfortunately, the required reagents are harmful and the reaction times are rather long. We investigated earlier the use of H₂O₂ as a more environmentally friendly oxidizing agent to replace the hazardous chromates. In the present study, we have furthered this possibility by incorporating the use of H₂O₂ in the presence of UV light. A protocol has been devised and tested with standards and real samples that replaces toxic Cr(VI), halves the amount of silver sulfate required, and greatly reduces the necessary reaction time, thus yielding a faster and more environmentally sound method.     

Studying the Effects of Two Various Methods of Composting on the Degradation Levels of Polycyclic Aromatic Hydrocarbons (PAHs) in Sewage Sludge

The research comprised of studying the effect composting sewage sludge with sawdust and vermicomposting with earthworm Eisenia fetida has on the degradation of 16 polycyclic aromatic hydrocarbons (PAHs). Raw rural sewage sludge prior composting was more contaminated with PAHs than urban sewage sludge, in both cases exceeding EU cutoff limits of 6 mg/kg established for land application. Dibenzo[a,h]anthracene (DBahAnt), acenaphtylene (Acy) and indeno[1,2,3-c,d]pyrene (IPyr) were predominant in rural sewage sludge, whilst the urban sewage sludge contained the highest concentrations of benzo[b]fluoranthene (BbFl), benzo[k]fluoranthene (BkFl) and indeno[1,2,3-c,d]pyrene (IPyr). Thirty days of composting with sawdust has caused a significant reduction of 16 PAHs on average from 26.07 to 4.01 mg/kg (84.6%). During vermicomposting, total PAH concentration decreased on average from 15.5 to 2.37 mg/kg (84.7%). Vermicomposting caused full degradation of hydrocarbons containing 2 and 6 rings and significant reduction of PAHs with 3 aromatic rings (94.4%) as well as with 5 aromatic rings (83.2%). The lowest rate of degradation (64.4%) was observed for hydrocarbons with 4 aromatic rings such as fluoranthene, benzo(a)anthracene, chrysene and pyrene. On the other hand, the highest level of degradation was determined for PAHs with 2 rings (100%), 3 rings (88%) and 6 aromatic rings in the molecule (86.9%) after composting with sawdust. Acenaphthene and pyrene were found to be the most resistant to biodegradation during both composting methods.     

Biochar-induced changes in soil properties affected immobilization/mobilization of metals/metalloids in contaminated soils

Purpose

Remediation of metal contaminated soil with biochar is attracting extensive interest in recent years. Understanding the significance of variable biochar properties and soil types helps elucidating the meticulous roles of biochar in immobilizing/mobilizing metals/metalloids in contaminated soils.

Materials and methods

Six biochars were produced from widely available agricultural wastes (i.e., soybean stover, peanut shells and pine needles) at two pyrolysis temperatures of 300 and 700 °C, respectively. The Pb-, Cu-, and Sb-contaminated shooting range soils and Pb-, Zn-, and As-contaminated agricultural soils were amended with the produced biochars. The mobility of metals/metalloids was assessed by the standard batch leaching test, principal component analysis and speciation modeling.

Results and discussion

The changes in soil properties were correlated to feedstock types and pyrolysis temperatures of biochars based on the principal component analysis. Biochars produced at 300 °C were more efficient in decreasing Pb and Cu mobility (>93 %) in alkaline shooting range soil via surface complexation with carboxyl groups and Fe-/Al-minerals of biochars as well as metal-phosphates precipitation. By contrast, biochars produced at 700 °C outperformed their counterparts in decreasing Pb and Zn mobility (100 %) in acidic agricultural soil by metal-hydroxides precipitation due to biochar-induced pH increase. However, Sb and As mobility in both soils was unfavorably increased by biochar amendment, possibly due to the enhanced electrostatic repulsion and competition with phosphate.

Conclusions

It is noteworthy that the application of biochars is not equally effective in immobilizing metals or mobilizing metalloids in different soils. We should apply biochar to multi-metal contaminated soil with great caution and tailor biochar production for achieving desired outcome and avoiding adverse impact on soil ecosystem.

     

Changes in organic carbon content and its physical and chemical distribution in paddy soils cultivated under different fertilisation practices

Purpose

Chemical protection facilitates soil organic carbon (SOC) sequestration and stabilisation due to a strong chemical binding with mineral surfaces and metal ions (e.g. iron [Fe], aluminium [Al] and calcium [Ca]). However, there is not much information regarding the role of chemical protection in SOC stabilisation in paddy soils, particularly in terms of the specific forms of organo-mineral complexes such as Fe-, Al- and Ca-bonded OC.

Materials and methods

We sampled paddy soils at the 0–20 cm soil layer from a long-term field experiment (initiated in 1981) conducted under humid subtropical conditions in China, which has five fertilisation treatments (i.e. control treatment without fertiliser [CK], chemical fertiliser only [CF], green manure [GM], Straw and Manure) with equivalent nutrient inputs (i.e. N, P₂O₅ and K₂O at the rates of 135–67.5–135 kg ha^?1, respectively, for both early and late rice) except CK. We determined the chemical binding forms of SOC and the associated soil properties in the particulate fraction (PF, >53 μm) and the mineral-associated fraction (MAF, <53 μm), which were obtained using a low-energy ultrasonic dispersion procedure, of a paddy soil in the long-term fertilisation experiment.

Results and discussion

Iron- and Al-bonded OC (Fe/Al-OC) was the dominant fraction and made up 55–70% of the total SOC in the paddy soil, while Ca-bonded OC (Ca-OC) was only a minor fraction (<4%). The Fe/Al-OC was mainly allocated in the MAF (52–67%), indicating that the chemical protection of SOC occurred mostly in the finer particle fractions. Long-term application of organic amendments increased the contents of bulk SOC by 27–34% (P < 0.05), of Fe/Al-OC by 9–16% and of Ca-OC by 35–83% (P < 0.05), whereas the sole application of chemical fertiliser had no significant effects on SOC contents of the paddy soil compared with the treatment without fertiliser inputs. Both amorphous Fe and Al extracted by ammonium oxalate (Fe_ox and Al_ox) showed significant correlations with Fe/Al-OC (r = 0.52 and 0.78, respectively), but Al_ox appeared to have a greater influence on C stabilisation in the paddy soil.

Conclusions

These results demonstrated that the dominant chemical binding forms of SOC in the paddy soils were Fe/Al-OC and amorphous Fe/Al oxyhydrates, especially amorphous Al, contributed mostly to the chemical stabilisation of SOC.

     

Characteristics of Nitrogen Loss through Surface-Subsurface Flow on Red Soil Slopes of Southeast China

Soil nitrogen (N) loss related to surface flow and subsurface flow (including interflow and groundwater flow) from slope lands is a global issue. A lysimetric experiment with three types of land cover (grass cover, GC; litter cover, LC; and bare land, BL) were carried out on a red soil slope land in southeast China. Total Nitrogen (TN) loss through surface flow, interflow and groundwater flow was observed under 28 natural precipitation events from 2015 to 2016. TN concentrations from subsurface flow on BL and LC plots were, on average, 2.7–8.2 and 1.5–4.4 times greater than TN concentrations from surface flow, respectively; the average concentration of TN from subsurface flow on GC was about 36–56% of that recorded from surface flow. Surface flow, interflow and groundwater flow contributed 0–15, 2–9 and 76–96%, respectively, of loss load of TN. Compared with BL, GC and LC intercepted 83–86% of TN loss through surface runoff; GC intercepted 95% of TN loss through subsurface flow while TN loss through subsurface flow on LC is 2.3 times larger than that on BL. In conclusion, subsurface flow especially groundwater flow is the dominant hydrological rout for N loss that is usually underestimated. Grass cover has the high retention of N runoff loss while litter mulch will increase N leaching loss. These findings provide scientific support to control N runoff loss from the red soil slope lands by using suitable vegetation cover and mulching techniques.     

Zirconium-Modified Activated Sludge as a Low-Cost Adsorbent for Phosphate Removal in Aqueous Solution

A highly effective zirconium-modified activated sludge (Zr(IV)-AS) adsorbent was prepared from activated sludge and applied to remove phosphate from aqueous solutions by batch and column experiments. Characterized results revealed that zirconium was successfully loaded onto the activated sludge (AS), and the specific surface area and pore volume were substantially improved after zirconium loading on the AS. Zr(IV)-AS exhibited a high adsorption affinity for phosphate and the maximum adsorption amount was 27.55 mg P·g^?1 at 25 °C. Adsorption isotherms of phosphate could be described by the Langmuir model, and the adsorption kinetics were well described by the pseudo-second-order model. Phosphate adsorption on Zr(IV)-AS increased monotonically with decreasing solution pH. The presence of SO₄^2? in water resulted in slightly decreased phosphate adsorption on the adsorbent even at a high concentration (25 mmol/L), and a greater influence of HCO₃^? on adsorption could be ascribed to the increased solution pH with the addition of the HCO₃^?. Column adsorption experimental results showed that the adsorbent has excellent phosphate adsorption properties and that the effluent can meet the requirement of phosphorus in the national wastewater discharge standard of China. Phosphate-saturated Zr(IV)-AS can be effectively desorbed in 0.1 mol L^?1 NaOH solution, and the regenerated adsorbent still possessed the high capacity. The adsorption between the adsorbent and the phosphate is due to the electrostatic interaction and anionic exchange at the surface of the Zr(IV)-AS. Furthermore, this approach provides a possibility of treating wastewater with waste and has the potential for industrial applications for the removal of phosphate from wastewater.     

Evaluation of palygorskite for remediation of Cd-polluted soil with different water conditions

Purpose

The study aimed at comparing the effects of different water managements on soil Cd immobilization using palygorskite, which was significant for the selection of reasonable water condition.

Materials and methods

Field experiment was taken to discuss the in situ remediation effects of palygorskite on Cd-polluted paddy soils, under different water managements, using a series of variables, including pH and extractable Cd in soils, plant Cd, enzyme activity, and microorganism number in soils.

Results and discussion

In control group, the pH in continuous flooding was the highest under three water conditions, and compared to conventional irrigation, continuous flooding reduced brown rice Cd by 37.9%, and brown rice Cd in wetting irrigation increased by 31.0%. In palygorskite treated soils, at concentrations of 5, 10, and 15 g kg^?1, brown rice Cd reduced by 16.7, 44.4, and 55.6%; 13.8, 34.5, and 44.8%; and 13.1, 36.8, and 47.3% under continuous flooding, conventional irrigation, and wetting irrigation (p < 0.05), respectively. The enzyme activity and microbial number increased after applying palygorskite to paddy soils.

Conclusions

Continuous flooding was a good candidate as water management for soil Cd stabilization using palygorskite. Rise in soil enzyme activity and microbial number proved that ecological function regained after palygorskite application.

     

Soil nitrogen availability alters rhizodeposition carbon flux into the soil microbial community

Purpose

Soil microorganisms are important in the cycling of plant nutrients. Soil microbial biomass, community structure, and activity are mainly affected by carbon substrate and nutrient availability. The objective was to test if both the overall soil microbial community structure and the community-utilizing plant-derived carbon entering the soil as rhizodeposition were affected by soil carbon (C) and nitrogen (N) availability.

Materials and methods

A ¹³C-CO₂ steady-state labeling experiment was conducted in a ryegrass system. Four soil treatments were established: control, amendment with carboxymethyl cellulose (CMC), amendment with ammonium nitrate (NF), combined CMC and NF. Soil phospholipid fatty acid (PLFA) and ¹³C labeling PLFA were extracted and detected by isotope ratio mass spectrometer.

Results and discussion

The combined CMC and NF treatment with appropriate C/N ratio (20) significantly enhanced soil microbial biomass C and N, but resulted in lower soil inorganic N concentrations. There was no significant difference in soil PLFA profile pattern between different treatments. In contrast, most of the ¹³C was distributed into PLFAs 18:2ω6,9c, 18:1ω7c, and 18:1ω9c, indicative of fungi and gram-negative bacteria. The inorganic-only treatment was distinct in ¹³C PLFA pattern from the other treatments in the first period of labeling. Factor loadings of individual PLFAs confirmed that gram-positive bacteria had relatively greater plant-derived C contents in the inorganic-only treatment, but fungi were more enriched in the other treatments.

Conclusions

Amendments with CMC can improve N transformation processes, and the ryegrass rhizodeposition carbon flux into the soil microbial community is strongly modified by soil N availability.

     

Effects of temperature on soil organic carbon fractions contents,aggregate stability and structural characteristics of humic substances in a Mollisol

Purpose

Under a global warming scenario, understanding the response of soil organic carbon fractions and aggregate stability to temperature increases is important not only for better understanding and maintaining relevant ecosystem services like soil fertility and crop productivity, but also for understanding key environmental processes intimately related with the maintenance of other regulatory ecosystem services like global climate change mitigation through carbon sequestration. An increase in temperature would accelerate the mineralization of soil organic carbon. However, the properties of organic carbon remained in soil after mineralization is not well known.

Materials and methods

Mollisol was collected at 0–20-cm depth from maize (Zea mays L.) field in Northeast China. A 180-day incubation experiment was conducted at three different temperatures (10, 30, and 50 °C) under constant soil moisture (60 % water holding capacity). Soil samples were assayed for total organic carbon (TOC), water-soluble organic carbon (WSOC), easily oxidizable organic carbon (EOC), humic fractions carbon, aggregate-associated carbon, and water stability of aggregates. Elemental analysis and solid-state ¹³C nuclear magnetic resonance spectroscopy were used to characterize humic acid and humin fractions.

Results and discussion

The contents of soil TOC, EOC, humic fractions carbon, and aggregate-associated carbon decreased with the increase in temperature. The proportion of 2–0.25-mm macroaggregate and the mean weight diameter (MWD) of aggregates also decreased. The C, H, N, S, alkyl C, and O-alkyl C contents of humic acid and humin decreased, whereas the O, aromatic C, and carbonyl C contents increased. The H/C, aliphatic C/aromatic C, and O-alkyl C/aromatic C ratios in humic acid and humin fractions decreased.

Conclusions

The increase in temperature has a negative impact on soil organic carbon content, soil aggregation, and aggregate stability. Moreover, humic acid and humin molecules become less aliphatic and more decomposed with the increase in temperature.

     

Atmospheric Mercury Fluxes in a Southern Boreal Forest and Wetland

Total gaseous mercury (TGM) fluxes from the forest floor and a boreal wetland were measured by a flux chamber technique coupled with an automatic mercury vapour analyser. The fluxes were measured at three sampling sites in southern Finland, 61°14′ N, 25°04′ E in summer 2007, with additionally in situ TGM concentrations in the air at one of the sites and mercury bulk deposition at another. Most of the flux data were collected during the daytime. At one of the sites, diurnal flux behaviour was studied, and a clear cycle with an afternoon maximum and a night minimum was observed. The highest emissions (up to 3.5 ng m⁻² h⁻¹) were observed at the forest floor site having a moss and grass cover. At the wetland and litter-rich forest floor sites, the emissions were below 1 ng m⁻² h⁻¹ and sometimes negative (down to −1.0 ng m⁻² h⁻¹), indicating mercury uptake. The measured average fluxes in August were 0.9 ± 1.1 and 0.2 ± 0.3 ng m⁻² h⁻¹ for the forest floor sites and wetland sites, respectively. The flux data were compared with the mercury bulk deposition, which proved to be of the same magnitude, but opposite in sign. At the mossy forest floor site, the extrapolated TGM emissions were 130% of the Hg deposition in August 2007. Comparison with other studies showed that the fluxes in background areas are relatively uniform, regardless of measurement site location and method used. Airborne TGM remained at the background level during the study, with an average value of 1.3 ± 0.2 ng m⁻³; it frequently showed a diurnal cycle pattern.