Composition and spectroscopic characteristics of dissolved organic matter extracted from the sediment of Erhai Lake in China

Purpose

The content and composition of dissolved organic matter (DOM) in sediment directly affect nutrient cycling and material exchange in lake ecosystems. This study investigated the content and composition of DOM and its fractions in sediments, as well as the relationship between the different parameters and nitrogen (N) forms in DOM. The main aim of this study was to evaluate the compositional characteristics of DOM, hydrophobic bases (HOB), hydrophobic acids (HOA), hydrophobic neutral fractions (HON), and hydrophilic matter (HIM) in sediments from Erhai Lake, China.

Materials and methods

Seven surface sediment samples with different environmental characteristics were collected. The DOM in the sediment was fractionated into HOB, HOA, HON, and HIM using XAD-8 resin based on compound hydrophobicity. The contents of DOM and its fractions were measured using a TOC analyzer. The structural characteristics of DOM and its fractions were investigated using fluorescence spectroscopy and UV–Vis absorbance. Correlation analyses were carried out to better understand the relationships between the parameters of the spectral characteristics and the contents of the different N forms in DOM and its fractions.

Results and discussion

The content, spatial distribution and structure of DOM and its fractions in Erhai Lake sediment were affected by water depth and aquatic plants. The DOM content in sediment ranged from 0.2 to 0.5 g kg^?1. HON accounted for 41.3 to 85.7 % of DOM, whereas HIM constituted 15.0 to 58.7 % and was significantly negatively correlated with HON (R ² ?=?0.856, P?Conclusions (1) Hydrophobic fractions are the major components of DOM in the sediments from the seven sites in Erhai Lake. (2) DOM and its fractions mainly originated from microbial sources. (3) The A ₂₅₃/A ₂₀₃ ratio is useful for evaluating the contents of N forms. The structure of DOM and its fractions are important in affecting the contents of DON. Nitrate (NO₃-N) contributes to eutrophication, and thus cannot be ignored from studies of Erhai Lake sediment.     

Electron transfer capacity of soil dissolved organic matter and its potential impact on soil respiration

Purpose

Soil dissolved organic matter (DOM) as the labile fraction of soil organic carbon (SOC) is able to facilitate biogeochemical redox reactions effecting soil respiration and carbon sequestration. In this study, we took soil samples from 20 sites differing in land use (forest and agriculture) to investigate the electron transfer capacity of soil DOM and its potential relationship with soil respiration.

Materials and methods

DOM was extracted from 20 soil samples representing different land uses: forest (nos. 1–12) and agriculture (nos. 13–20) in Guangdong Province, China. Chronoamperometry was employed to quantify the electron transfer capacity (ETC) of the DOM, including electron acceptor capacity (EAC) and electron donor capacity (EDC), by applying fixed positive or negative potentials to a working electrode in a conventional three-electrode cell. The reversibility of electron accepting from or donating to DOM was measured by applying switchable potentials to the working electrode in the electrochemical system with the multiple-step potential technique. Carbon dioxide produced by soil respiration was measured with a gas chromatograph.

Results and discussion

Forest soil DOM samples showed higher ETC and electron reversible rate (ERR) than agricultural soil DOM samples, which may be indicative of higher humification rate and microbial activity in forest soils. The average soil respiration of forest soil (nos. 1–12) and agricultural soil (nos. 13–10) was 26.34 and 18.58 mg C g^?1 SOC, respectively. Both EDC and EAC of soil DOM had close relationship with soil respiration (p?<?0.01). The results implied that soil respiration might be accelerated by the electroactive moieties contained in soil DOM, which serve as electron shuttles and facilitate electron transfer reactions in soil respiration and SOC mineralization.

Conclusions

DOM of forest soils showed higher ETC and ERR than DOM of agricultural soils. As soil represents one of the largest reservoirs of organic carbon, soil respiration affects C cycle and subsequently CO₂ concentration in the atmosphere. As one of the important characteristics of soil DOM related to soil respiration, ETC has a significant impact on greenhouse gas emission and soil carbon sequestration but has not been paid attention to.     

Optimization of arsenic and pentachlorophenol removal from soil using an experimental design methodology

Purpose

In this study, a soil-washing process was investigated for arsenic (As) and pentachlorophenol (PCP) removal from polluted soils. This research first evaluates the use of chemical reagents (HCl, HNO₃, H₂SO₄, lactic acid, NaOH, KOH, Ca(OH)₂, and ethanol) for the leaching of As and PCP from polluted soils.

Materials and methods

A Box–Behnken experimental design was used to optimize the main operating parameters for soil washing. A laboratory-scale leaching process was applied to treat four soils polluted with both organic ([PCP] _i ?=?2.5–30 mg kg^?1) and inorganic ([As] _i ?=?50–250 mg kg^?1, [Cr] _i ?=?35–220 mg kg^?1, and [Cu] _i ?=?80–350 mg kg^?1) compounds.

Results and discussion

Removals of 72–89, 43–62, 52–68, and 64–98 % were obtained for As, Cr, Cu, and PCP, respectively, using the optimized operating conditions ([NaOH]?=?1 N, [cocamidopropylbetaine] _i ?=?2 % w w^?1, t?=?2 h, T?=?80 °C, and PD?=?10 %).

Conclusions

The use of NaOH, in combination with the surfactant, is efficient in reducing both organic and inorganic pollutants from soils with different levels of contamination.     

Can root exudate components influence the availability of pyrene in soil?

Purpose

Little information is currently available regarding the influence of different root exudate components (RECs) on the availability of persistent organic pollutants in the soil environment. In this study, we investigated the impacts of different RECs including organic acids, amino acids, and fructose on the availability of pyrene as a representative polycyclic aromatic hydrocarbon (PAH) in soils.

Materials and methods

Citric acid, oxalic acid, malic acid, serine, alanine, and fructose were used in the experiments as representative RECs. Pyrene-spiked soils (TypicPaleudalfs) with present RECs were incubated for 30 days, and the available fraction of pyrene was determined using n-butanol extraction procedure.

Results and discussion

The amount of n-butanol-extractable pyrene in soil increased with the addition of tested RECs and increased when REC concentrations are enhanced within the range of 0–21 g kg^?1. The extractability of pyrene in soil with REC treatments and the enhancement ratio (r, %) of the extractable pyrene in soil by the addition of RECs after a 30-day incubation decreased in the following order: organic acids (oxalic acid ≥ citric acid > malic acid) > amino acid (alanine > serine) > fructose. This decrease was observed irrespective of soil sterilization, although the concentrations of extractable pyrene were lower in non-sterilized soils compared to sterilized soils. The concentrations of metal cations and dissolved organic matter (DOM) in solution increased when organic acids were added.

Conclusions

The tested RECs at concentrations of 0–21 g kg^?1 clearly enhanced the availability of pyrene in soils, and larger amounts of RECs resulted in higher pyrene availabilities in the tested soils. Microbial biodegradation diminished the amount of available pyrene irrespective of the presence of RECs. The mechanism of REC-influenced availability of pyrene in soil may be related to the metal dissolution and release of DOM from soil solids. The results of this study will be useful in assessing PAH-related risks to human health and the environment and will be instructive in food safety and remediation strategies at contaminated sites.     

Application of ionic liquids for the extraction and passive sampling of endocrine-disrupting chemicals from sediments

Purpose

The aim of this study was to assess the applicability of ionic liquids (ILs) in the extraction of organic contaminants from sediments and in passive sampling as a receiving phase material.

Materials and methods

Solutions of two water-soluble ionic liquids (WSILs)—1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIm]BF₄) and N-butyl-3-methyl pyridinium tetrafluoroborate ([BMPy]BF₄)—were used for the extraction of endocrine-disrupting chemicals (EDCs), including bisphenol A (BPA), 17β-estradiol (E2), and nonylphenol (NP), from different sediments. Furthermore, a hydrophobic IL (1-hexadecyl-3-methyl imidazolium hexafluorophosphate) was filled in a polyethylene (PE) membrane tubing to build an IL-PE passive sampler for sediment pore water. Uptake kinetics were studied by exposing samplers to sediments artificially contaminated by EDCs and identified by exposing samplers to field-contaminated sediments.

Results and discussion

EDCs were efficiently extracted by WSIL solutions from the two artificially contaminated sediments, with maximum extraction efficiencies of 84.2–104.6 % by the [BMIm]BF₄ solution and 74.9–103.7 % by the [BMPy]BF₄ solution. However, WSIL solutions are not suitable for EDC extraction from sediment with very low organic carbon contents. EDCs in sediment pore water can be efficiently taken up by the IL-PE sampler, with uptake rate constants of 2.08?×?10^?2?l?g^?1?day^?1 (BPA), 5.74?×?10^?2?l?g^?1?day^?1 (E2), and 2.10 l?g^?1?day^?1(NP).

Conclusion

BPA, E2, and NP can be extracted efficiently by IL water solution from most of the artificially and field-contaminated sediments used in this study. The IL ([HDMIm]PF₆)-PE passive sampler can be used to monitor EDCs in the pore water of sediments. A good match between the calculated and measured concentrations of BPA and E2 in pore water of field-contaminated sediments was observed.     

Carbon and nitrogen turnover in response to warming and nitrogen addition during early stages of forest litter decomposition—an incubation experiment

Purpose

Little is known about the interactive effects of temperature, nitrogen (N) supply, litter quality, and decomposition time on the turnover of carbon (C) and N of forest litter. The objective of this study was to investigate the interactive effects of warming, N addition and tree species on the turnover of C and N during the early decomposition stage of litters in a temperate forest.

Materials and methods

A 12-week laboratory incubation experiment was carried out. The leaf litters including two types of broadleaf litters (Quercus mongolica and Tilia amurensis), a needle litter (Pinus koraiensis), and a mixed litter of them were collected from a broad-leaved Korean pine mixed forest ecosystem in northeastern China in September 2009. Nine treatments were conducted using three temperatures (15, 25, and 35 °C) combined with three doses of N addition (equal to 0, 75, and 150 kg?·?ha^?1?a^?1, respectively, as NH₄NO₃).

Results and discussion

After 12 weeks of incubation, the mass loss ranged between 12 and 35 %. The broadleaf litters had greater mass loss and cumulative CO₂–C emission than the needle litter. Temperature and N availability interacted to affect litter mass loss and decomposition rate. The dissolved organic carbon (DOC) and nitrogen (DON) concentrations in litter leachate varied widely with litter types. DOC increased significantly with increased temperature but decreased significantly with increased N availability. DON increased significantly with increased N availability but showed a higher level at the moderate decomposition temperature. The amounts of CO₂ and N₂O emission were significantly higher at 25 °C than those at 15 and 35 °C, and were significantly increased by the N addition.

Conclusions

The present study indicated relatively intricate temperature and N addition effects on C and N cycling during early stages of litter decomposition, implying that future increases in temperature and N deposition will directly affect C and N cycling in broad-leaved Korean pine mixed forest ecosystem, and may indirectly influence the ecosystem composition, productivity, and functioning in NE China. It is, therefore, important to understand the interactive effects of biotic and abiotic factors on litter decomposition in field conditions in order to assess and predict future ecosystem responses to environmental changes in NE China.     

Production and consumption of N2O during denitrification in subtropical soils of China

Purpose

Nitrous oxide (N₂O) production and reduction rates are dependent on the interactions with each other and it is therefore important to evaluate them within the context of simultaneously operating N₂O emission and reduction. The objective of this study was to quantify the simultaneously occurring N₂O emission and reduction across a range of subtropical soils in China, to gain a mechanistic understanding of potential N₂O dynamics under the denitrification condition and their important drivers, and to evaluate the potential role of the subtropical soils as either sources or sinks of N₂O through denitrification.

Materials and methods

Soils (45, from a range of different land uses and soil parent materials) were collected from the subtropical region of Jiangxi Province, China, and tested for their potential capacity for N₂O emission and N₂O reduction to N₂ during denitrification. N₂O emission and reduction were determined in a closed system under N₂ headspace after the soils were treated with 200?mg?kg^?1 NO ₃ ^? -N and incubation at 30?°C for 28?days. The soil physical and chemical properties, the temporal variations in headspace N₂O concentration, and NO ₃ ^? -N and NH ₄ ⁺ -N concentrations in the soil slurry were measured.

Results and discussion

Variations in N₂O concentration (N) over incubation time (t) were consistent with an equation in which average R ²?=?0.84?±?0.11 (p?<?0.05): $ N = A \times \left( {1 - \exp \left( { - {k_1} \times t} \right)} \right) - B \times \exp \left( {{k_2} \times t} \right) $ , where A is the total N₂O emission during the incubation, B is a constant, and k ₁ and k ₂ are the N₂O emission constant and reduction constants, respectively. The results of the simulation showed that k ₁ was greater than k ₂. The reduced amount of NO ₃ ^? -N in the first 7?days of incubation and the N₂O emission rate (the percentage of A value relative to the amount of NO ₃ ^? -N reduced during the 28-day incubation, R _n) were able to explain 82.9?% (p?<?0.01) of the variation in total N₂O emission (A) during the incubation for the soil samples studied, indicating that the total amount of N₂O emitted was determined predominately by denitrification capacity. Soil organic carbon content and soil nitrogen mineralization are the key factors that determine differences in the amounts of reduced NO ₃ ^? -N among the soil samples. The R _n value decreased with increasing k ₂ (p?<?0.01), indicating that soils with higher N₂O reduction capacity under these incubation conditions would emit less N₂O per unit of denitrified NO ₃ ^? -N than the other soils. Results are valuable in the evaluation of net N₂O emissions in the subtropical soils and the global N budget.

Conclusions

In a closed, anaerobic system, variations in N₂O concentration in the headspace over the incubation time were found to be compatible with a nonlinear equation. Soil organic carbon and the amount of NH ₄ ⁺ -N mineralized from the organic N during the first 7?days of incubation are the key factors that determine differences in the N₂O emission constant (k ₁), the N₂O reduction constant (k ₂), the total N₂O emission during the incubation (A) and the N₂O emission rate (R _n).     

Extraction and speciation analysis of roxarsone and its metabolites from soils with different physicochemical properties

Purpose

The application of roxarsone (ROX), an arsenic-containing compound, as a feed additive in the animal production industry results in elevated soil levels of ROX and its metabolites, namely, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenate (As(V)), and arsenite (As(III)). This study was conducted to study the extraction and speciation analysis of ROX-related arsenicals in soils with different physicochemical properties and the possible effects of soil properties on the extraction of ROX and its metabolites.

Materials and methods

Analytical method based on high-performance liquid chromatography (HPLC)-inductively coupled plasma–mass spectrometry (ICP-MS) was employed to determine the concentrations of As(III), DMA, MMA, As(V), and ROX extracted by different extraction solvents from different soils spiked by arsenicals. Validity of the developed method was assessed by the recovery efficiencies of arsenic species in soil-dissolved matter solutions containing 20 μg As?·?L^?1 of each arsenic species. Effects of soil properties on the extraction of ROX and its metabolites were analyzed by Pearson’s correlation.

Results and discussion

Arsenic species were separated using gradient elution of water and 20 mmol?·?L^?1 (NH₄)₂HPO₄ + 20 mmol?·?L^?1 NH₄NO₃ + 5 % methanol (v/v) within 27 min. The linear ranges of all arsenicals were 0–200 μg As?·?L^?1 with R ²?>?0.9996. The developed method provided lower limits of detection for As(III), DMA, MMA, As(V), and ROX (0.80, 0.58, 0.35, 0.24, and 1.52 μg As?·?L^?1, respectively) and excellent recoveries (92.52–102.2 %) for all five species. Arsenic speciation was not altered by 0.1 mol?·?L^?1 NaH₂PO₄ + 0.1 mol?·?L^?1 H₃PO₄ (9:1, v/v), which offered better average extraction efficiencies for As(III), As(V), DMA, MMA, and ROX (32.49, 92.50, 78.24, 77.64, and 84.54 %, respectively). Extraction performance of arsenicals was influenced by soil properties, including pH, cation exchange capacity (CEC), total Fe, and amorphous Fe.

Conclusions

ROX and its metabolites from soils could be satisfactorily separated by the developed method for the studied arsenicals. To extract arsenic species from soils, 0.1 mol?·?L^?1 NaH₂PO₄ + 0.1 mol?·?L^?1 H₃PO₄ (9:1, v/v) was recommended. Extraction efficiencies of arsenicals were influenced more by solvent composition than soil physicochemical properties. The present study provides a valuable tool and useful information for determining the concentrations of ROX and its metabolites in contaminated soils.

     

Methane and nitrous oxide emissions as affected by organic–inorganic mixed fertilizer from a rice paddy in southeast China

Purpose

The effects of commercial compost fertilizer application on trace gas emissions are not well understood due to a lack of field experiments. The objective of this study was to evaluate the emissions of methane (CH₄) and nitrous oxide (N₂O) along with grain yield from a rice paddy as affected by different organic–inorganic mixed fertilizer (OIMF) treatments.

Materials and methods

A field experiment was initiated in 2006 with chemical compound fertilizer (CF) and three OIMF amendments including pig manure compost (PMC), Chinese medicine residue compost (CMC), and rapeseed cake compost (RCC), from a rice paddy in southeast China. The emissions of CH₄ and N₂O were simultaneously measured using the static opaque chamber method over the entire rice growing season in 2011. Soil biotic parameters were measured in soil collected after the rice was harvested in 2011.

Results and discussion

Relative to the control, the OIMF treatments significantly increased CH₄ emissions by 56–99 %, mainly due to exogenous organic substrate input, whereas no difference was observed in the CF treatment. The N₂O emissions were stimulated substantially by an average of 40 % due to nitrogen fertilization compared with the control. Consecutive OIMF application tended to increase the grain yield, making it marginally higher than that of the CF treatment (7 %, P?=?0.06). Compared with the control, the CF treatment slightly decreased the global warming potential and greenhouse gas (GHG) intensity, while they were remarkably increased in the OIMF treatments. Over the 5-year period of 2006–2011, the annual soil carbon sequestration rate was estimated to be 1.19 t C ha^?1 year^?1 for the control and 1.73–1.98 t C ha^?1 year^?1 for the fertilized treatments.

Conclusions

Our results suggest that despite the beneficial effects of increasing both grain yield and soil organic matter, OIMF application such as PMC, CMC, and RCC may be responsible for increased global warming due mainly to the stimulated CH₄ emissions. This effect should be thus taken into account when balancing agricultural production and GHG mitigation.     

Simultaneous measurement of soil organic and inorganic carbon: evaluation of a thermal gradient analysis

Purpose

The best method for determining soil organic carbon (SOC) in carbonate-containing samples is still open to debate. The objective of this work was to evaluate a thermal gradient method (ThG), which can determine simultaneously inorganic carbon (SIC) and SOC in a wide range of soil samples.

Materials and methods

The determination of SOC by ThG (SOC_ThG) was compared to the following widespread standard methods: (1) acidification (ACI) as pretreatment and subsequent dry combustion (SOC_ACI) and (2) volumetric quantification of SIC by a calcimeter (CALC) and subtraction of the total carbon content as determined by dry combustion (SOC_CALC). Precision (F test) and bias (t test) were tested on a subset of seven samples (n?=?3). Comparison of the ThG and CALC methods was performed by regression analysis (n?=?76) on samples representing a wide range of SOC (5.5 to 212.0 g kg^?1) and SIC (0 to 59.2 g kg^?1) contents.

Results and discussion

Tests on the replicated subset showed that the precision of ThG was not significantly different from ACI or CALC (F values?<?39, n?=?3) for SOC and SIC measurements. However, SOC_ACI and SOC_CALC contents were systematically and significantly lower compared to SOC_ThG contents. The positive bias for SOC_ThG relative to SOC_CALC contents appeared also in the regression analysis (given numbers?±?standard errors) of the whole data set (y?=?(4.67?±?0.70)?+?(0.99?±?0.01)x, R ²?=?0.99, n?=?76). When performing a regression with carbonate-free samples, the bias between the methods was negative (?2.90?±?0.63, n?=?29) but was positive in the set with carbonate-containing samples (3.95?±?1.41, n?=?47). This observation corroborated the suspicion that the use of acid for carbonate decomposition can lead to an underestimation of SOC.

Conclusions

All methods were suitable for differentiation between SIC and SOC, but the use of acid resulted in lower estimates of SOC contents. When comparing soil samples with different carbonate concentrations, the use of the ThG method is more reliable.     

Changes of labile and recalcitrant carbon pools under nitrogen addition in a city lawn soil

Purpose

Carbon (C) flux is largely controlled by the highly bio-reactive labile C (LC) pool, while long-term C storage is determined by the recalcitrant C (RC) pool. Soil nitrogen (N) availability may considerably affect changes of these pools. The aim of this study was to investigate the effects of N treatments on soil LC and RC pools.

Materials and methods

A field experiment was conducted in a city lawn soil for 600 days with three N treatments, i.e., the control (0 kg N ha^?1 year^?1), low-N (100 kg N ha^?1 year^?1), and high-N (200 kg N ha^?1 year^?1) treatments. As the N source, NH₄NO₃ solution was added to soil surface monthly. Measurements of LC, RC, and other soil biochemical properties, including pH, soil respiration rates, microbial biomass, and enzymes activities, were taken during the experiment period.

Results and discussion

The low-N and high-N treatments increased 6.3 and 13% of the LC pool, respectively, which was caused by decreased microbial biomass and soil respiration rates under the N treatments. By contrary, the low-N and high-N treatments decreased 5.9 and 12% of the RC pool, respectively. The N addition treatments enhanced phenol oxidase activities. The enhanced oxidase activities decreased new RC input and the increased dissolved organic C stimulated RC pool decomposition. The LC and RC pools were highly influenced by the N treatments, whereas effect of the N treatments on soil organic C was not significant. The N addition treatments also caused soil acidification and reduced bacterial biomass proportion in the soil microbial composition.

Conclusions

The N addition increased the LC pool but decreased the RC pool in the soil. These changes should greatly impact soil long-term C storage.     

Links between vegetation patterns, soil C and N pools and respiration rate under three different land uses in a dry Mediterranean ecosystem

Purpose

Soil respiration (R _s) is controlled by abiotic soil parameters interacting with characteristics of the vegetation and the soil microbial community. Few studies have attempted a comprehensive approach that simultaneously addresses the roles of all the major factors known to influence R _s. Our goal was to explore the links between heterogeneity in R _s, aboveground plant biomass and belowground properties in three representative land-use types in a dry Mediterranean ecosystem: (1) a 150-year-old mixed Aleppo pine-kermes oak open forest, (2) an abandoned agricultural field, which was cultivated with cereal for several years until abandonment in 1980, when establishment of typical Mediterranean shrubland vegetation started and (3) a rain-fed olive grove, which has been cultivated for 100 years.

Materials and methods

We selected two distinctive sampling periods coinciding with annual minimum or near minimum (December) and maximum (April) rates of R _s in this dry Mediterranean ecosystem. In each sampling period, R _s, temperature and moisture, aboveground plant biomass, carbon (C) and nitrogen (N) contents in both light and heavy soil organic matter fractions, extractable dissolved organic C (EDOC), as well as microbial and fine root biomass were measured within each land-use type.

Results and discussion

Across sites, R _s rates were significantly higher in April (3.07?±?0.1 μmol?m^?2?s^?1) than in December (1.30?±?0.1 μmol?m^?2?s^?1). The labile soil organic matter fractions (light fraction C and N contents, microbial biomass C and EDOC) were consistently and strongly related to one another, and to a lesser extent, to the C and N contents in the heavy fraction across sites and seasons. Linear models adequately explained a large proportion of the within-site variability in R _s (R ² values ranged from 41 to 91 % depending on land use and season) but major controls on R _s differed considerably between sites and seasons. Primary controls on spatial patterns in R _s were linked to recent plant-derived C inputs in both forest and olive grove sites. However, in the abandoned agricultural field site R _s appeared to be mainly driven by microbial activity, which could be sustained by intermediate or recalcitrant C and N pools derived from previous land use.

Conclusions

Conversion of native woodland to agricultural land and subsequent land abandonment leads to profound changes in the relationships between R _s, aboveground biomass and belowground properties in this dry Mediterranean ecosystem. While above- and belowground vegetation are the primary controls on spatial variability in labile soil C pools and R _s in the open forest and olive grove sites, a complete lack of influence of current vegetation patterns on soil C pools and respiration rates in the abandoned agricultural field was observed.     

Desorption and distribution of pentachlorophenol (PCP) on aged black carbon containing sediment

Purpose

There is a strong affinity between organic compounds and black carbon (BC) in sediments, but the release of adsorbed organic compounds from BC may vary with the duration of contaminant–sediment contact (i.e., aging). The objective of this paper was to evaluate the effect of the application of rice straw carbon (RC) on the control of hydrophobic ionizable organic compounds (HIOCs) pollution and investigate whether aging affects the release of adsorbed pentachlorophenol (PCP) in RC-amended sediment.

Materials and methods

Two experiments were conducted in this study: Tenax-mediated desorption kinetics experiment and PCP’s distribution experiment over aging time. The Tenax-mediated desorption kinetics data were fit with a modified two-domain model. PCP’s distribution pools in sediment involves water soluble (F ₁), 48 h desorption (F ₂), 432 h desorption minus 48 h desorption (F ₃), strongly complexed (F ₄), and nonextractable fractions (F ₅).

Results and discussion

A good fit of the desorption kinetics data was obtained with the modified two-domain model, and R ² ranged from 0.979 to 0.999. The presence of RC in the sediment reduced the rapid and slow desorption fractions (F _rap and F _slow) as well as the rapid and slow rates of desorption of PCP (k _rap and k _slow) from the sediment, and the RC also increased the desorption-resistant fraction (F _r ). F _rap and F _slow both increased, while F _r decreased after aging. The PCP content of F ₁, F ₂, and F ₃ increased but decreased in F ₄ and F ₅ with contact time. Furthermore, the segregation of PCP varied less with aging time in sediments with 2.0 % RC than in sediments with 0.5 % RC.

Conclusions

RC played a dominant role in hindering PCP mass transfer and reducing PCP availability in sediments. After the RC-amended sediment was aged for 98 days, the PCP was released more easily and became more readily available, which was attributed primarily to the RC–sediment aging rather than of the PCP–sediment aging. Furthermore, 0.5 % RC is not sufficient to control PCP release from sediments, and 2.0 % RC is needed to fix PCP in sediments over long periods of time.     

Organic anion-to-acid ratio influences pH change of soils differing in initial pH

Purpose

This study aimed to investigate the effect of initial soil pH and organic anion-to-acid ratio on changes in soil pH.

Materials and methods

Two soils (Podosol and Tenosol) along with two carboxylic acids (malic and citric acid) and their anions (sodium malate and citrate), commonly found in plant residues, were used in this study. Stock solutions of either malic acid and disodium malate or citric acid and trisodium citrate were added to pre-incubated soils at anion-to-acid ratios of 0:100, 10:90, 25:75, 50:50, 75:25, 90:10, 100:0 and at 0.25 g C kg^?1 soil. Soils were adjusted to 80 % field capacity and mixed thoroughly, and three replicates of 50 g of each soil were transferred into individual plastic cores and incubated at 25 °C in the dark for 30 days. Soil pH, respiration, NH₄ ⁺, and NO₃ ^? were determined.

Results and discussion

Soil pH increased linearly with increasing organic anion-to-acid ratio. The addition of organic anions to soil resulted in net alkalinisation. However, the addition of organic acids immediately decreased soil pH. During subsequent incubation, soil pH increased when the organic anions were decomposed. Alkalinity generation was lower in the Podosol (initial pH 4.5) than in the Tenosol (initial pH 6.2), and was proportional to anion-to-acid ratio across all the treatments. Cumulative CO₂-C release was approximately three times lower in the Podosol than the Tenosol at day 2 due to lower microbial activity in the low-pH Podosol.

Conclusions

Increasing anion-to-acid ratio of organic compounds increased soil pH. Increases in soil pH were mainly attributed to direct chemical reactions and decomposition of organic anions. Low pH decreased the amount of alkalinity generated by addition of organic compounds due to incomplete decomposition of the added compounds. This study implies that organic anion-to-acid ratio in plant residues plays an important role in soil pH change.     

Total concentrations of heavy metals and occurrence of antibiotics in sewage sludges from cities throughout China

Purpose

A total of 58 dewatered sludge samples were collected from 58 sewage treatment plants (STPs) geographically located in 31 provincial cities of China; the concentrations of heavy metals and antibiotics were determined to monitor the pollutant levels on a large scale, and the pollutant concentrations in sludge samples from different sources of sewage sludge and different geographical regions were compared.

Materials and methods

All the samples were divided into two portions, one of which was air-dried for determination of heavy metals. The other portion was placed in a brown glass bottle and frozen at ?20 °C for antibiotics analysis. Total heavy metals were digested with aqua regia and determined by atomic absorption spectrophotometry (Varian SpectrAA 220FS and Varian SpectrAA 220Z). The antibiotics were extracted with EDTA-sodium phosphate buffer with acetonitrile/Mg(NO₃)₂-NH₃?H₂O, v/v, 3:1 and analysed by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) and quantified by the isotope-labelled internal standard method.

Results and discussion

In all the sludge samples, zinc was the most abundant metal followed by copper, with relatively low concentrations of chromium, lead, nickel and cadmium. Only 20 % of samples exceeded the Chinese class A values of heavy metal standards for agricultural use (GJ/T309-2009). Sixteen different antibiotics were detected in all the sludge samples, and fluoroquinolones (FQs) and tetracyclines (TCs) were more abundant than sulfonamides (SAs). Concentrations of ∑FQs, ∑TCs and ∑SAs ranged from 1,569 to 23,825 μg kg^?1 (mean 8,274 μg kg^?1, dry weight), from 592 to 37,895 μg kg^?1 (mean 8,326 μg kg^?1, dry weight) and from 20.1 to 117 μg kg^?1 (mean 55.4 μg kg^?1, dry weight), respectively. Tetracyclines (except chlortetracycline) were significantly correlated with zinc and lead. No significant regional trends were observed in the concentrations of heavy metals and antibiotics in sludges.

Conclusions

Heavy metal concentrations are not the major factor restricting domestic and mixed flow sludge application, but the antibiotic concentrations in sludges are problematic; regulation of antibiotic use and establishment of standards to ensure safe handling of sludges are needed.     

Influence of mixtures of acenaphthylene and benzo[a]anthracene on their degradation by Pleurotus ostreatus in sandy soil

Purpose

Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds commonly found as soil contaminants. Fungal degradation is considered as an environmentally friendly and cost-effective approach to remove PAHs from soil. Acenaphthylene (Ace) and Benzo[a]anthracene (BaA) are two PAHs that can coexist in soils; however, the influence of the presence of each other on their biodegradation has not been studied. The biodegradation of Ace and BaA, alone and in mixtures, by the white rot fungus Pleurotus ostreatus was studied in a sandy soil.

Materials and methods

Experimental microcosms containing soil spiked with different concentrations of Ace and BaA were inoculated with P. ostreatus. Initial (t ₀) and final (after 15 days of incubation) soil concentrations of Ace and BaA were determined after extraction of the PAHs.

Results and discussion

P. ostreatus was able to degrade 57.7% of the Ace in soil spiked at 30 mg kg^?1 dry soil and 65.8% of Ace in soil spiked at 60 mg kg^?1 dry soil. The degradation efficiency of BaA by P. ostreatus was 86.7 and 77.4% in soil spiked with Ace at 30 and 60 mg kg^?1 dry soil, respectively. After 15 days of incubation, there were no significant differences in Ace concentration between soil spiked with Ace and soil spiked with Ace + BaA, irrespective of the initial soil concentration of both PAHs. There were also no differences in BaA concentration between soil spiked with BaA and soil spiked with BaA + Ace.

Conclusions

The results indicate that the fungal degradation of Ace and BaA was not influenced by the presence of each other’s PAH in sandy soil. Bioremediation of soils contaminated with Ace and BaA using P. ostreatus is a promising approach to eliminate these PAHs from the environment.     

Toxicity of arsenic in relation to soil properties: implications to regulatory purposes

Purpose

The present work evaluates the influence of different soil properties and constituents on As solubility in laboratory-contaminated soils, with the aim of assessing the toxicity of this element from the use of bioassays to evaluate the soil leachate toxicity and thereby propose soil guideline values for studies of environmental risk assessment in soil contamination.

Materials and methods

Seven soils with contrasting properties were artificially contaminated in laboratory with increasing concentrations of As. Samples were incubated for 4 weeks, and afterwards, soil solution (1:1) was obtained after shaking for 24 h. The soil leachate toxicity was assessed with two commonly used bioassays (seed germination test with Lactuca sativa and Microtox ® test with Vibrio fischeri).

Results and discussion

The relationship between soluble As and soil properties indicated that iron oxides and organic matter content were the variables most closely related to the reduction of the As solubility, while pH and CaCO₃ increased As solubility in the soil solutions. Toxicity bioassays showed significant differences between soils depending on their properties, with a reduction of the toxicity in the iron-rich soil (no observed effect concentration (NOEC)?=?150 mg kg^?1) and a significant increase in the highly carbonate samples (NOEC between 15 and 25 mg kg^?1).

Conclusions

Soil guideline values for regulatory purposes usually set a single value for large areas (regions or countries) which can produce over- or underestimation of efforts in soil remediation actions. These values should consider different levels according to the main soil properties controlling arsenic mobility and the soil leachate toxicity.     

Effect of biosolid application to Mollisol Chilean soils on the bioavailability of heavy metals (Cu,Cr, Ni,and Zn) as assessed by bioassays with sunflower (Helianthus annuus) and DGT measurements

Purpose

This study assessed the effect of biosolid application on the bioavailable fraction of some trace elements (Cu, Cr, Ni, and Zn) using a bioassay with sunflower (Helianthus annuus) and a chemical assay, diffusion gradient in thin films (DGT).

Materials and methods

Five surface soil samples (0–20 cm) were collected from an agricultural zone in Central Chile where biosolids are likely to be applied. Municipal biosolids were mixed with the soil at concentrations of 0, 30, 90, and 200 Mg ha^?1. The experiment to determine the bioavailability of metals in the soil using the bioassay was performed using sunflower. The DGT technique and Community Bureau of Reference (BCR) sequential extraction were used to determine the bioavailable fractions of the metals.

Results and discussion

The application of biosolids increased the phytoavailability of Zn, Ni, and Cr in most of the soils, as indicated by the increasing concentrations in sunflower plants as the biosolid application rate increased. In two of the soils, Codigua and Pelvín, this increase peaked at an application rate of 90 Mg ha^?1. Decreases in the bioavailable fractions of Zn, Ni, and Cr were observed with higher biosolid application rates. The bioavailability of metals was estimated through multiple linear regression models between the metals in the sunflower plants and the different chemical fractions of metals in the soils treated with different biosolid rates, which displayed a positive contribution of the labile (water soluble, carbonate, and exchangeable), oxide, and organic metal forms in the soil, particularly with respect to Ni and Zn at application rates of 30 and 90 Mg ha^?1. The bioavailable fraction of metals was determined in soils using the DGT technique. The effective concentration (C _E) results were compared with those in sunflower plants. The DGT technique could effectively predict the bioavailable fractions of Cr, Ni, and Zn in the Taqueral soil but only that of Zn in the Polpaico soil.

Conclusions

The application of biosolids significantly increased the labile fraction of most of the metals in the studied soils, particularly at the highest biosolid application rate. C _E increased as the concentration of biosolids increased for most of the metals. The effectiveness of the DGT technique for predicting the bioavailability of metals was dependent on the soil type and the metal. However, the C _E for soil Cu was not related to plant Cu for all soils studied.     

Nitrification and acidification from urea application in red soil (Ferralic Cambisol) after different long-term fertilization treatments

Purpose

Long-term manure applications can prevent or reverse soil acidification by chemical nitrogen (N) fertilizer. However, the resistance to re-acidification from further chemical fertilization is unknown. The aim of this study was to examine the effect of urea application on nitrification and acidification processes in an acid red soil (Ferralic Cambisol) after long-term different field fertilization treatments.

Materials and methods

Soils were collected from six treatments of a 19-year field trial: (1) non-fertilization control, (2) chemical phosphorus and potassium (PK), (3) chemical N only (N), (4) chemical N, P, and K (NPK), (5) pig manure only (M), and (6) NPK plus M (NPKM; 70 % N from M). In a 35-day laboratory incubation experiment, the soils were incubated and examined for changes in pH, NH₄ ⁺, and NO₃ ^?, and their correlations from urea application at 80 mg N kg^?1(?80) compared to 0 rate (?0).

Results and discussion

From urea addition, manure-treated soils exhibited the highest acidification and nitrification rates due to high soil pH (5.75–6.38) and the lowest in the chemical N treated soils due to low soil pH (3.83–3.90) with no N-treated soils (pH 4.98–5.12) fell between. By day 35, soil pH decreased to 5.21 and 5.81 (0.54 and 0.57 unit decrease) in the NPKM-80 and M-80 treatments, respectively, and to 4.69 and 4.53 (0.43 and 0.45 unit decrease) in the control-80 and PK-80 treatments, respectively, with no changes in the N-80 and NPK-80 treatments. The soil pH decrease was highly correlated with nitrification potential, and the estimated net proton released. The maximum nitrification rates (K _max) of NPKM and M soils (14.7 and 21.6 mg N kg^?1 day^?1, respectively) were significantly higher than other treatments (2.86–3.48 mg N kg^?1 day^?1). The priming effect on mineralization of organic N was high in manure treated soils.

Conclusions

Field data have shown clearly that manure amendment can prevent or reverse the acidification of the red soil. When a chemical fertilizer such as urea is applied to the soil again, however, soil acidification will occur at possibly high rates. Thus, the strategy in soil N management is continuous incorporation of manure to prevent acidification to maintain soil productivity. Further studies under field conditions are needed to provide more accurate assessments on acidification rate from chemical N fertilizer applications.     

Effect of Abiotic and Biotic Factors on the Photo-Induced Production of Dissolved Gaseous Mercury

This study was conducted to evaluate the contribution of environmental factors such as solar radiation and dissolved organic matter (DOM) on the photo-induced dissolved gaseous mercury (DGM) production through laboratory experiments using field water samples collected from wetlands. DGM production was more significantly influenced by UVB intensity than UVA. DGM formation was also significantly affected by DOM chemical structure/composition rather than its concentration. Increasing NO ₃ ^? concentration limited DGM production, but photo-induced Hg oxidation stimulated by NO ₃ ^? would possibly occur when the NO ₃ ^? level is more than twice the DOC level. The addition of phosphorus into the field water samples induced a slight increase of DGM production; however, the addition of nitrogen decreased DGM formation, suggesting that an increase of limiting nutrients in water may promote biotic DGM production. Experiments using a Selenastrum capricornutum monoculture solution showed that cell density had a positive effect on DGM production. Moreover, the difference in DGM production between filtered and unfiltered samples showed that S. capricornutum significantly produced biotic DGM under UVA irradiation. Finally, our results imply that environmental factors such as light intensity, DOM sources, and site-specific microorganisms can significantly affect photo-induced Hg transformation.