Kinetic and Thermodynamic Studies of Chlorinated Organic Compound Degradation by Siderite-Activated Peroxide and Persulfate

The efficacy of two oxidant systems, iron-activated hydrogen peroxide (H₂O₂) and iron-activated hydrogen peroxide coupled with persulfate (S₂O₈ ^2?), was investigated for treatment of two chlorinated organic compounds, trichloroethene (TCE) and 1,2-dichloroethane (DCA). Batch tests were conducted at multiple temperatures (10–50 °C) to investigate degradation kinetics and reaction thermodynamics. The influence of an inorganic salt, dihydrogen phosphate ion (H₂PO₄ ^?), on oxidative degradation was also examined. The degradation of TCE was promoted in both systems, with greater degradation observed for higher temperatures. The inhibition effect of H₂PO₄ ^? on the degradation of TCE increased with increasing temperature for the iron-activated H₂O₂ system but decreased for the iron-activated hydrogen peroxide-persulfate system. DCA degradation was limited in the iron-activated hydrogen peroxide system. Conversely, significant DCA degradation (87% in 48 h at 20 °C) occurred in the iron-activated hydrogen peroxide-persulfate system, indicating the crucial role of sulfate radical (SO₄ ^??) from persulfate on the oxidative degradation of DCA. The activation energy values varied from 37.7 to 72.9 kJ/mol, depending on the different reactants. Overall, the binary hydrogen peroxide-persulfate oxidant system exhibited better performance than hydrogen peroxide alone for TCE and DCA degradation.     

Quantifying soil macropore networks in different forest communities using industrial computed tomography in a mountainous area of North China

Purpose

Macropores have important effects on the movement of soil water, air, and chemical substances. However, the quantitative relationship between complex 3D soil macropore networks and forest communities remains unclear in the northern mountainous area in China. The objectives of this study were to (1) use industrial computed tomography (CT) scanning and image analysis to quantitatively analyze macropore networks in intact soil columns and (2) identify characteristics of soil macropore networks in different forest communities.

Materials and methods

Intact soil columns (100-mm diameter, 300 mm long) were taken from six local forest communities with three replicates for a total of 18 samples. Industrial X-ray CT was used to scan soil samples; then, the scanned images were used to obtain the 3D images of rock fragments and macropore structures. Next, the macropore structure was quantified, including volume, diameter, surface area, length, angle, tortuosity, and number of macropores. This technique provided an accurate method to quantify the structure of macropores.

Results and discussion

The analysis and results revealed that different forest communities influence soil macropore 3D structure significantly and in different ways. Macropores in mixed Pinus tabulaeformis, Castanea mollissima, and Ulmus pumila forest had the largest diameter, surface area, network density, and length density of macropores as well as the smallest mean tortuosity of soil macropores. This is caused by the fact that mixed forest soils had more complex root systems, better soil structure, and more biotic activity. Within the soils of a single forest community, macropore porosity, network density, surface area density, and length of macropores decreased with increased soil depth, because more roots and more biological activity were present in the surface soil.

Conclusions

Advanced industrial CT technology can allow an accurate quantification of soil macropore structure. This is important because this type of structure has significant effects on soil water, air, and chemical transport. The results suggest that mixed forest is the best afforestation model in the northern mountainous area in China because of its ability to improve soil structure.

     

Soil pH,organic matter,and nutrient content change with the continuous cropping of <Emphasis Type="Italic">Cunninghamia lanceolata</Emphasis> plantations in South China

Purpose

Chinese fir (Cunninghamia lanceolata (Lamb.) Hook) is an important native tree species in China. Consecutive cropping traditionally occurs in Chinese fir plantations (CFPs), but this practice has resulted in productivity declines in subsequent rotations. This study was designed to better understand the change of soil properties in the continuous cropping CFPs.

Materials and methods

We investigated soil pH, soil organic matter (SOM), and nutrient contents in different soil layers and in rhizosphere soil (RS) and non-rhizosphere soil (NRS) under CFPs of different ages and in different rotations.

Results and discussion

In the upper (0–20 cm) soil layer, soil pH decreased, while SOM increased, beneath mature CFPs with consecutive rotations. Total nitrogen (TN), available potassium, and available phosphorus contents in the upper soil layers did not differ significantly with consecutive rotations. Soil pH in RS was significantly lower than in NRS under mature plantations of the third rotation. Soil organic matter, TN, and available nitrogen did not differ between RS and NRS. Available phosphorus in RS was consistently lower than in NRS, and was highly deficient in the third rotation.

Conclusions

We conclude that no severe soil nutrient degradation occurred in the continuous cropping CFPs examined in this study, with soil acidification and phosphorus deficiency being two primary problems observed.

     

Sedimentary records of the Zrmanja River estuary,eastern Adriatic coast—natural vs. anthropogenic impacts

Purpose

Investigations of geochemical characteristics of sediments of the Zrmanja River estuary were done in order to determine the natural and anthropogenic factors influencing sediment composition in this area. For that purpose, spatial and temporal distribution of major and trace elements in the sediments and surrounding soils was studied.

Materials and methods

Sediment and soil samples, including one marl sample, were collected at 28 locations. All samples were subjected to total digestion and subsequently analysed by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for total concentration of 20 elements (Ag, Al, As, Be, Ca, Cd, Co, Cr, Cu, Fe, Li, Mn, Ni, Pb, Rb, Sb, Sn, Sr, Ti and Y). Obtained concentrations and their normalized counterparts were used for assessment of factors influencing sedimentation in the study area.

Results and discussion

The results of the analysis showed that the composition of sediments of the Zrmanja River estuary is primarily determined by the composition of bedrock, existing hydrodynamic conditions and the relative isolation of the studied basin. Nevertheless, anthropogenic influences were observed as well. The composition of the Zrmanja River sediments reflects the impact of the ex-alumina factory “Jadral” and transfer by wind of the material from its immediate surroundings to the water system of the Zrmanja River. In addition, sedimentation in the Zrmanja River was found to be influenced by the construction of reservoirs and the HE “Velebit”, hydroelectric power plant located in the Zrmanja watershed.

Conclusions

The geochemical composition of recent sediments of the Zrmanja River estuary is controlled primarily by natural factors, although the influence of anthropogenic activities is also evident.

     

Simultaneous immobilization of lead,cadmium, and arsenic in combined contaminated soil with iron hydroxyl phosphate

Purpose

Combined contamination of lead (Pb), cadmium (Cd), and arsenic (As) in soils especially wastewater-irrigated soil causes environmental concern. The aim of this study is to develop a soil amendment for simultaneous immobilization of Pb, Cd, and As in combinative contaminated soil.

Materials and methods

A soil amendment of iron hydroxyl phosphate (FeHP) was prepared and characterized, and its potential application in simultaneous immobilization of Pb, Cd, and As in combined contaminated soil from wastewater-irrigated area was evaluated. The effects of FeHP dosage, reaction time, and soil moisture on Pb, Cd, and As immobilization in the soil were examined.

Results and discussion

The immobilization efficiencies of Pb, Cd, and As generally increased with the increasing of FeHP dosage. With FeHP dosage of 10 %, the immobilization percentages of NaHCO₃-extractable As and DTPA-extractable Pb and Cd reached 69, 59, and 44 %, respectively. The equilibrium time required for immobilization of these contaminants was in the following order: NaHCO₃-extractable As (0.25 days) < DTPA-extractable Cd(3 days) < DTPA-extractable Pb (7 days). However, the immobilization efficiencies of Pb, Cd, and As have not changed much under soil moisture varied from 20 to 100 %. According to the results of the sequential extraction, the percentages of Pb, Cd, and As in residual fractions increased after the application of FeHP amendment, while their percentages in exchangeable fractions decreased, illustrating that FeHP can effectively decrease the mobilities and bioavailabilities of Pb, Cd, and As in the soil. Moreover, the application of FeHP will not have soil acidification and soil structure problem based on the soil pH measurements and soil morphology.

Conclusions

FeHP can immobilize Pb, Cd, and As in the combinative contaminated soil from wastewater irrigation area simultaneously and effectively. Thus, it can be used as a potential soil amendment for the remediation of Pb, Cd, and As-combined contaminated soil.

     

Soil CO<Subscript>2</Subscript> sources above a subterranean cave—Pisani rov (Postojna Cave,Slovenia)

Purpose

The objective of this research is to detect abiotic sources of soil CO₂ above a subterranean cave in the Slovenian karst region.

Materials and methods

The research was performed in the forest above Pisani rov (Postojna Cave) near the town of Postojna (SW Slovenia) and also in the cave. Soil gas, atmospheric air and cave air carbon stable isotope composition (δ¹³C_CO2) and CO₂ concentration were measured. Sampling and measurements were performed bi-monthly at the test and control sites above the cave. The abiotic source of soil CO₂ was estimated using a stable isotope mass balance calculation.

Results and discussion

Similar seasonal patterns of soil CO₂ and δ¹³C_CO2 values were observed at both the test and control sites until spring, with higher levels of CO₂ observed in summer and lower in winter. The δ¹³C_CO2 showed the opposite trend, i.e. lower values (?26 to ?20 ‰) in summer and higher values (up to ?17 ‰) in winter and early spring. In spring, the soil CO₂ concentration decreases and the δ¹³C_CO2 value increases only at the control site. A time series of a modelled “isotopically light” endmember revealed large shifts in the data values, due to the presence of an abiotic CO₂ source. Results suggest that the subterranean CO₂ pool and its ventilation is the main source of soil CO₂, accounting for up to 80 % of the soil gas during cold periods.

Conclusions

Ventilation from subterranean cavities is an important source of soil CO₂ in karstic areas and should be taken into account during carbon cycling studies.

     

Sediment transport below a small alpine reservoir desilted by controlled flushing: field assessment and one-dimensional numerical simulation

Purpose

Sediment transport and riverbed sedimentation were investigated in an alpine stream below a small hydropower reservoir desilted by a controlled sediment flushing (CSF) operation. The term “controlled” refers to the operational tasks implemented to mitigate the downstream environmental impact of the operation. The experimental dataset acquired before, during, and after the CSF was also used to carry out and calibrate a one-dimensional sediment transport model of the monitored event.

Materials and methods

The investigated reservoir is located in the central Italian Alps, and its original storage was 160,000 m³, about 30% filled by a mixture of sand and silt/clay before the CSF. Downstream sediment concentration was controlled by releasing clear water from upstream reservoirs and regulating the work of earth-moving equipment in the emptied reservoir. A 3.6-km-long reach with average slope of 0.015 was monitored: concentration and grain size of suspended sediment were measured during the CSF and the riverbed alteration was evaluated by volumetric sampling and measurements of the deposits’ thickness. Sedimentation and River Hydraulics—One Dimensional (SRH-1D) was used to simulate sediment transport during the monitored CSF. Model parameters were calibrated by comparing the computed and the observed amount of sediment deposited along the study reach.

Results and discussion

Sediment flushing was carried out in October 2010 for 3 days. Ca. 16,000 m³ of sediment were evacuated, representing approximately 30% silt/clay and 70% sand. 2.4 Mm³ of clear water was released to reduce sediment concentration and increase transport capacity downstream. About 3000 m³ of sand was deposited in the study reach after the CSF, with maximum height up to 0.2 m. Although the riverbed before the CSF was simply set as mono-granular, after calibrating the parameters, good agreement was achieved between the depositional pattern computed by SRH-1D and the one observed, both in terms of deposit thickness and grain size of deposited sediment. The sensitivity analysis revealed a major role of the parameters controlling bed mixing processes in affecting the simulated deposition after the CSF.

Conclusions

Sediment below 0.1 mm in diameter was not detected in river deposits after the flushing: the effects on river biota associated with substrate clogging by very fine sediment were therefore minimized. After proper calibration, 1-D sediment transport modeling can effectively support the planning of CSF operations: to minimize the downstream environmental effects, concurrently achieving acceptable flushing efficiency, the analyzed scenarios as well as the model outputs need to be carefully evaluated from a multidisciplinary perspective.

     

Effects of ionic surfactants on the aggregate stability and water repellency of silt loam soil

Purpose

With the increase of surfactant usages, more and more concerns were paid on their effects on the physicochemical characteristics of soils. Up to now, only few researches have examined the effects of ionic surfactants on the stability of soil structure and soil water repellency.

Materials and methods

Cetyltrimethyl ammonium bromide (CTAB) as cationic surfactant and sodium dodecyl sulfate (SDS) as anionic surfactant were adopted to investigate their effects on the aggregate stability and water repellency of a silt loam soil which was sampled in Corn High-Tech Park, Huang-Huai-Hai region, China. (1) Aggregate stability: 50 g soil was mixture with 100 mL surfactant solution in a beaker. The concentrations of surfactant solutions were 0 (the blank), 200, 400, 600, 800, 1000, and 2000 mg L^?1, respectively. After 30 min, the soil was sieved and divided into four fraction aggregates. (2) Soil water repellency: the concentrations of surfactant solutions were the same as experiment 1. Forty grams of soil was blended with 80 mL surfactant solution in an aluminum specimen. Drying the water by oven of 40 °C firstly and then by air, the whole period was about 1 week. After that, soil water infiltration and sorptivity were measured.

Results and discussion

Compared to the blank, surfactants increased the amounts of 2–0.25 and <0.053 mm aggregates of the soil and decreased the amounts of 0.25–0.053 mm aggregates of the soil. Surfactants also increased the mean weight diameter (MWD) of the soil. Except the 200 mg L^?1 treatment, CTAB promoted the soil water infiltration. All SDS treatments impeded the soil water infiltration. The soil repellency factor (R) value of the blank was 1.22, lower than the critical value of 1.95, which implied that the soil of blank treatment was free of soil water repellency. For CTAB, only 200 and 400 mg L^?1 treatment’s R were higher than 1.95 while for SDS, all the treatment’s R were higher than 1.95.

Conclusions

Surfactants improved the stability of soil aggregates. Soil treated with CTAB did not show the repellency, whereas SDS treatment resulted in intense water repellency compared with the wettable blank soil. Findings of this study can be used to explain the role of ionic surfactants on soil structure stability as well as on the development of water repellency in lower soil depths.

     

Patterns and drivers of fungal diversity along an altitudinal gradient on Mount Gongga,China

Purpose

Fungi are essential components of soil microbial communities and have a crucial role in biogeochemical processes. Alpine regions are sensitive to climate change, and the importance of changes in fungal community composition along altitudinal gradients in alpine regions is hotly debated.

Materials and methods

We used 454 pyrosequencing approaches to investigate the fungal communities at 1600, 2300, 2800, 3000, and 3900 m above sea level along an altitudinal gradient on Mount Gongga.

Results and discussion

The results showed that Agaricomycetes, Sordariomycetes, and Tremellomycetes are the dominant classes at all sampling sites. Operational taxonomic unit richness decreased with increasing altitude, and the fungal communities were clustered into three groups that corresponded to altitudes of, i.e., 1600, 2300, and above 2800 m. The evenness of fungi was not significantly correlated with altitude, whereas beta diversities were significantly correlated with altitude. The distance-based redundancy analysis and Mantel test indicated that the composition of fungal assemblages was mostly driven by altitude and temperature.

Conclusions

Our results indicated that ecological processes possibly related to altitude and temperature play an important role in structuring fungal biodiversity along the elevational gradient. Our results highlight that different microbes may respond differently to environmental gradients.

     

Soil chemical and biochemical properties of a salt-marsh alluvial Spanish area after long-term reclamation

Marisma, one of the largest salt-marsh alluvial areas in SW Spain, has been reclaimed since 1970 by artificial drainage and amendment with phosphogypsum (PG) so as to reduce Na⁺ saturation. Within the reclaimed area, two 250- × 20-m plots were treated as follows: (1) amendment with 25 Mg/ha of PG every 2 to 3 years between 1979 and 2003 (plot PY); (2) like PY but PG treatment stopped after 1997 (plot DR). A contiguous virgin Marisma salt-marsh plot (MV), neither drained nor amended, was the control. In MV, soil microbial biomass C, most enzyme activities and total organic C content were much greater than in PY and DR soils, despite the salinity stress. The decrease in soil organic matter content in PY and DR soils was likely due to cotton-cropping practices, which favoured the organic C mineralisation and nutrients removal by crops. Microbial activity of MV soil, probably stimulated by the rhizodepositions of the natural vegetation, did not suffer from the osmotic effect due to the raising of soil solution ionic strength. Microbial quotient could be ranked as MV > PY > DR, whereas the metabolic quotient had an opposite trend. Thus, both quotients suggested that the interruption of PG amendment was not favouring microbial activity. Principal component analysis clearly identified the chemical and biochemical soil properties mostly affected by the reclamation and also indicated the longer PG amendment in PY plot. Stepwise discriminant analysis identified two physiologically different types of soil microflora, one less active present in the MV virgin soil and another more active present in the reclaimed PY and DR soils.