Spatial uncoupling of biodegradation, soil respiration, and PAH concentration in a creosote contaminated soil

Hotspots and coldspots of concentration and biodegradation of polycyclic aromatic hydrocarbons (PAHs) marginally overlapped at the 0.5-100 m scale in a creosote contaminated soil in southern Sweden, suggesting that concentration and biodegradation had little spatial co-variation. Biodegradation was substantial and its spatial variability considerable and highly irregular, but it had no spatial autocorrelation. The soil concentration of PAHs explained only 20-30% of the variance of their biodegradation. Soil respiration was spatially autocorrelated. The spatial uncoupling between biodegradation and soil respiration seemed to be governed by the aging of PAHs in the soil, since biodegradation of added ¹³C phenanthrene covaried with both soil respiration and microbial biomass. The latter two were also correlated with high concentrations of phospholipid fatty acids (PLFAs) that are common in gram-negative bacteria. However, several of the hotspots of biodegradation coincided with hotspots for the distribution of a PLFA indicative of fungal biomass.     

Quantification of centimeter-scale spatial variation in PAH, glucose and benzoic acid mineralization and soil organic matter in road-side soil

The aim of the study was to determine centimeter-scale spatial variation in mineralization potential in diffusely polluted soil. To this end we employed a 96-well microplate method to measure the mineralization of ¹⁴C-labeled organic compounds in deep-well microplates and thereby compile mineralization curves for 348 soil samples of 0.2-cm³. Centimeter-scale spatial variation in organic matter and the mineralization of glucose, benzoic acid, and PAHs (phenanthrene and pyrene) was determined for urban road-side soil sampled as arrays (7 × 11 cm) of 96 subsamples. The spatial variation in mineralization was visualized by means of 2-D contour maps and quantified by means of semivariograms. The geostatistical analysis showed that the easily degradable compounds (glucose and benzoic acid) exhibited little spatial variation in mineralization potential, whereas the mineralization was highly heterogeneous for the PAH compounds that require specialized degraders. The spatial heterogeneity should be taken into account when estimating natural attenuation rates.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

超声波/紫外线-Fenton反应联用去除克拉玛依土壤中石油类污染物

研究了超声波(ultrasonic)和紫外线(ultraviolet)-Fenton反应联用处理干旱区老化石油污染土壤。土壤TPH含量为30 470 mg/kg,pH值为3,H2O2与Fe比例为50∶1时,H2O2浓度为0.37%、0.74%、1.11%和1.85%在超声波处理6 h土壤TPH去除量分别为4 495、11 983、15 470和19 800 mg/kg;TPH去除量随H2O2/Fe2+增大而增大,H2O2/Fe2+为100∶1时,TPH去除量为12 699 mg/kg。溶液pH值接近中性,H2O2浓度为0.74%,H2O2/Fe2+为50∶1,超声波与UV共同作用2 h和4 h,TPH去除量分别达到14 824和21 821 mg/kg;UV单独作用2 h、4 h对土壤TPH去除量为9 253和12 845 mg/kg。超声波-Fenton反应对1,2-二甲苯降解效果最好,其次为C17-C28的直链及支链烷烃,最低为烃类衍生物。     

Identifying sources of soil inorganic pollutants on a regional scale using a multivariate statistical approach: role of pollutant migration and soil physicochemical properties

Principal components analysis (PCA) and correlation analysis were used to estimate the contribution of four components related to pollutant sources on the total variation in concentrations of Cu, Zn, Pb, Cd, As, Se, Hg, Fe and Mn in surface soil samples from a valley in east China with numerous copper and zinc smelters. Results indicate that when carrying out source identification of inorganic pollutants their tendency to migrate in soils may result in differences between the pollutant composition of the source and the receptor soil, potentially leading to errors in the characterization of pollutants using multivariate statistics. The stability and potential migration or movement of pollutants in soils must therefore be taken into account. Soil physicochemical properties may offer additional useful information. Two different mechanisms have been hypothesized for correlations between soil heavy metal concentrations and soil organic matter content and these may be helpful in interpreting the statistical analysis.     

零价铁与双氧水异相Fenton降解活性艳橙X-GN

采用Fe0与H2O2构成异相Fenton体系降解偶氮染料活性艳橙X-GN,考察了初始pH、H2O2和Fe0投加量、温度等对反应过程的影响。实验结果表明,在初始pH值为3.0、Fe0投加量为0.8 g/L、H2O2投加量为5 mmol/L和反应温度30℃的条件下,反应60 min后活性艳橙降解率达到96.2%。Fe0与H2O2投加量都存在一个最佳范围,当Fe0与H2O2浓度大于0.8 g/L和5 mmol/L时,羟基自由基会通过其他方式消耗,致使活性艳橙降解率下降。酸性条件和提高温度均有利于反应的进行。反应符合准一级动力学,表观反应速率常数k为0.064 min-1(30℃),反应活化能为80.62 kJ/mol。UV-Vis光谱扫描表明,反应过程中活性艳橙的发色基团及苯环结构均被破坏。     

AhR agonist and genotoxicant bioavailability in a PAH-contaminated soil undergoing biological treatment

Background, aim, and scope  Degradation of the 16 US EPA priority PAHs in soil subjected to bioremediation is often achieved. However, the PAH loss is not always followed by a reduction in soil toxicity. For instance, bioanalytical testing of such soil using the chemical-activated luciferase gene expression (CALUX) assay, measuring the combined effect of all Ah receptor (AhR) activating compounds, occasionally indicates that the loss of PAHs does not correlate with the loss of Ah receptor-active compounds in the soil. In addition, standard PAH analysis does not address the issue of total toxicant bioavailability in bioremediated soil. Materials and methods  To address these questions, we have used the CALUX AhR agonist bioassay and the Comet genotoxicity bioassay with RTL-W1 cells to evaluate the toxic potential of different extracts from a PAH-contaminated soil undergoing large-scale bioremediation. The extracts were also chemically analyzed for PAH16 and PCDD/PCDF. Soil sampled on five occasions between day 0 and day 274 of biological treatment was shaken with n-butanol with vortex mixing at room temperature to determine the bioavailable fraction of contaminants. To establish total concentrations, parts of the same samples were extracted using an accelerated solvent extractor (ASE) with toluene at 100°C. The extracts were tested as inducers of AhR-dependent luciferase activity in the CALUX assay and for DNA breakage potential in the Comet bioassay. Results  The chemical analysis of the toluene extracts indicated slow degradation rates and the CALUX assay indicated high levels of AhR agonists in the same extracts. Compared to day 0, the bioavailable fractions showed no decrease in AhR agonist activity during the treatment but rather an up-going trend, which was supported by increasing levels of PAHs and an increased effect in the Comet bioassay after 274 days. The bio-TEQs calculated using the CALUX assay were higher than the TEQs calculated from chemical analysis in both extracts, indicating that there are additional toxic PAHs in both extracts that are not included in the chemically derived TEQ. Discussion  The response in the CALUX and the Comet bioassays as well as the chemical analysis indicate that the soil might be more toxic to organisms living in soil after 274 days of treatment than in the untreated soil, due to the release of previously sorbed PAHs and possibly also metabolic formation of novel toxicants. Conclusions  Our results put focus on the issue of slow degradation rates and bioavailability of PAHs during large-scale bioremediation treatments. The release of sorbed PAHs at the investigated PAH-contaminated site seemed to be faster than the degradation rate, which demonstrates the importance of considering the bioavailable fraction of contaminants during a bioremediation process. Recommendations and perspectives  It has to be ensured that soft remediation methods like biodegradation or the natural remediation approach do not result in the mobilization of toxic compounds including more mobile degradation products. For PAH-contaminated sites this cannot be assured merely by monitoring the 16 target PAHs. The combined use of a battery of biotests for different types of PAH effects such as the CALUX and the Comet assay together with bioavailability extraction methods may be a useful screening tool of bioremediation processes of PAH-contaminated soil and contribute to a more accurate risk assessment. If the bioremediation causes a release of bound PAHs that are left undegraded in an easily extracted fraction, the soil may be more toxic to organisms living in the soil as a result of the treatment. A prolonged treatment time may be one way to reduce the risk of remaining mobile PAHs. In critical cases, the remediation concept might have to be changed to ex situ remediation methods.     

Determination of anthropogenic boundary depth in industrially polluted soil and semi-quantification of heavy metal loads using magnetic susceptibility

This study focuses on magnetic susceptibility processing and analysis towards fast and cost-efficient discrimination and semi-quantification of anthropogenic heavy metal loads in soil. Spatial variability of magnetic susceptibility was investigated on sets of soil cores from both “polluted” and “less polluted” forest soil close to a steel mill near Leoben, Austria. Test sites of ∼10 m² represent “site scale” dimensions. Statistical analysis of magnetic data provides a boundary depth indicating the transition from the “polluted” to the deeper, “unpolluted” zone in contaminated natural soil. Introduction of a block master curve simplifies the complex variations of individual curves, and represents magnetic susceptibility at “site scale”. For linking the block master curve to heavy metals we only require magnetic susceptibility data from one soil core and heavy metal data from two sub-samples from the same core. Our optimized magnetic susceptibility data processing scheme provides an applicable tool to semi-quantify anthropogenic heavy metal loads in soil.     

Effect of microbial activity, soil water content and added copper on the temporal distribution patterns of HCB and DDT among different soil organic matter fractions

Temporal changes in the distribution of exogenous HCB and DDT among different soil organic matter fractions were studied under sterile and non-sterile conditions, different soil water contents, and different concentrations of added Cu(2+). The residence time was 311days. Soil organic matter was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions by a methyl isobutyl ketone (MIBK) method. Results revealed that there is a mass transfer tendency of DDT and HCB from FA, HA and BHA to IR and lipid fractions with increasing residence time. Microbial activity accelerated the mass transfer, while the addition of Cu(2+) slowed it down. The HCB and DDT transfer rate decreased as the soil moisture increased from 1.9% to 60%, but increased when soil moisture increased further to 90%. A two-compartment first order kinetic model was used to describe the mass transfer from FA, HA and BHA.     

PAH-sequestration capacity of granular and powder activated carbon amendments in soil, and their effects on earthworms and plants

A field lysimeter study was carried out to investigate whether the amendment of 2% powder and granular activated carbon (PAC and GAC) to a soil with moderate PAH contamination had an impact on the PAH bioaccumulation of earthworms and plants, since AC is known to be a strong sorbent for organic pollutants. Furthermore, secondary effects of AC on plants and earthworms were studied through growth and nutrient uptake, and survival and weight gain. Additionally, the effect of AC amendments on soil characteristics like pH, water holding capacity, and the water retention curve of the soil were investigated. Results show that the amendment of 2% PAC had a negative effect on plant growth while the GAC increased the growth rate of plants. PAC was toxic to earthworms, demonstrated by a significant weight loss, while the results for GAC were less clear due to ambiguous results of a field and a parallel laboratory study. Both kinds of AC significantly reduced biota to soil accumulation factors (BSAFs) of PAHs in earthworms and plants. The GAC reduced the BSAFs of earthworms by an average of 47 ± 44% and the PAC amendment reduced them by 72 ± 19%. For the investigated plants the BSAFs were reduced by 46 ± 36% and 53 ± 22% by the GAC and PAC, respectively.     

芬顿和氯化铁协同修复三价砷污染土的稳定化效果

由于铁盐稳定化修复砷污染土通常不考虑砷价态对毒性和迁移性的影响,导致了修复效果欠佳。针对三价砷污染土提出了预氧化-稳定化协同修复方法,先使用芬顿将三价砷氧化为低迁移性的五价砷,再利用氯化铁将其稳定化。通过合成沉降淋滤试验、生物可利用性、pH测试、连续萃取试验和光谱分析研究了协同修复的稳定化效果和机理。结果表明,与未经处理的污染土相比,1%用量的芬顿和1倍铁砷比的氯化铁进行协同修复的稳定化处理可使浸出浓度降低99.6%,生物可利用性砷的质量分数降低99.4%,修复效率得到提高;芬顿氧化和氯化铁稳定化都使土壤pH降低,但1倍铁砷比下协同修复后的pH为5.82,高于6倍铁砷比下只用氯化铁修复的pH (3.78) ,由此可一定程度上避免过量使用铁盐造成的土壤酸化;连续萃取试验表明协同修复后更多不稳定态的砷转变为稳定形态;光谱分析发现协同修复可以将土壤中三价砷全部氧化为五价,并通过铁氧化物/氢氧化物吸附和砷酸铁沉淀的形式固定砷。本研究结果可为三价砷污染土修复提供理论和技术支持。     

A microcosm approach to assessing the effects of earthworm inoculation and oat cover cropping on CO2 fluxes and biological properties in an amended semiarid soil

We designed a microcosm experiment to assess the influence of inoculation with Eisenia foetida earthworms and the establishment of an Avena sativa cover crop on biological (enzyme activities and labile carbon fractions) soil quality indicators in a soil treated with a composted organic residue, and to determine the contribution of these treatments to carbon dioxide emissions from the soil to the atmosphere of the microcosm. The microcosms were incubated for 53 days under 28 °C/18 °C day/night temperatures. The addition of earthworms and the planting of A. sativa increased dehydrogenase activity of compost amended soil by about 44% after 23 days of incubation. The metabolic potential, calculated as the ratio dehydrogenase activity/water soluble C, was higher in the compost amended soil planted with A. sativa. The highest total amount of CO₂–C evolved occurred in the soil treated with composted residue and earthworms (about 40% of the total amount of CO₂ evolved came from earthworm activity). The planting of A. sativa increased the decomposition rate constant of organic matter in the amended soil but decreased the potentially mineralizable C pool. In conclusion, the establishment of an A. sativa cover crop and the addition of E. foetida to a degraded agricultural soil treated with composted residue were effective treatments for improving the biological and biochemical quality and the metabolic potential of the soil.     

Extraction of arsenic in a synthetic arsenic-contaminated soil using phosphate

An environment-friendly and cost-effective extraction method has been studied for the removal of arsenic from contaminated soil. A yellow-brown forest soil was contaminated with arsenic(V) and used as a model soil. Among various potassium and sodium salts, potassium phosphate was most effective in extracting arsenic, attaining more than 40% extraction in the pH range of 6–8 with minimum damage to the soil properties. Exchange mechanism is proposed for the extraction of arsenic from soil by phosphate. Sequential extraction shows that phosphate is effective in extracting arsenic of Al- and Fe-bound forms. Arsenic of residual form was not extracted. Arsenic was efficiently extracted by phosphate solution of pH 6.0 at 300 mM phosphate concentration and at 40°C.     

Solubilization of lead and cadmium during the percolation of EDTA through a soil polluted by smelting activities

EDTA was percolated in laboratory columns through a soil polluted by heavy metals to investigate the efficiency of and processes involved in soil decontamination by chemical extraction. At high EDTA concentration (10⁻² M), elution of Pb and Cd was very efficient for one pore volume, after which it decreased to almost zero due to depletion of available Pb and Cd and to competition with Ca and Fe slowly solubilized during the passage of the EDTA front. Clogging occurred after the end of the EDTA plateau. At lower EDTA concentrations (10⁻³ and 10⁻⁴ M), elution was less efficient, but extraction decreased little with the volume percolated; moreover no Ca above background values was dissolved. The optimum EDTA concentration for heavy metal extraction ranges between 10⁻² and 10⁻³ M. The higher the concentration, the greater the extraction efficiency, but as the EDTA concentration is increased there is an optimum point at which clogging takes place and permeability decreases.     

Effects of mussel shell addition on the chemical and biological properties of a Cambisol

The use of a by-product of the fisheries industry (mussel shell) combined with cattle slurry was evaluated as soil amendment, with special attention to the biological component of soil. A wide number of properties related to soil quality were measured: microbial biomass, soil respiration, net N mineralization, dissolved organic carbon, dissolved organic nitrogen, dissolved inorganic nitrogen, dehydrogenase, β-glucosidase, urease and phosphomonoesterase activities. The amendments showed an enhancement of soil biological activity and a decrease of aluminium held in the cation exchange complex. No adverse effects were observed on soil properties. Given that mussel shells are produced in coastal areas as a by-product and have to be managed as a waste and the fertility constraints in the local soils due to their low pH, our research suggest that there is an opportunity for disposing a residue into the soil and improving soil fertility.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

Fenton and Fenton-like oxidation of pesticide acetamiprid in water samples: Kinetic study of the degradation and optimization using response surface methodology

The aims of this study were (a) to evaluate the degradation of acetamiprid with the use of Fenton reaction, (b) to investigate the effect of different concentrations of H₂O₂ and Fe²⁺, initial pH and various iron salts, on the degradation of acetamiprid and (c) to apply response surface methodology for the evaluation of degradation kinetics.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

Biotic transformation of anticoccidials in soil using a lab-scale bio-reactor as a precursor-tool

Two anticoccidial agents, salinomycin and robenidine, heavily used in the worldwide veterinary meat production, were investigated for their potential biotic degradation by cultured soil bacteria. The degradation-study was performed in lab-scale bio-reactors under aerobic and anaerobic conditions incubated for 200 h with a mixed culture of soil bacteria. Samples were analyzed by LC-MS/MS and potential transformation products were tentatively identified. Salinomycin was degraded under aerobic conditions and traces could be found after 200 h, however, seems more persistent under anaerobic conditions. Four transformation products of salinomycin were discovered. Robenidine was degraded under aerobic and anaerobic conditions, however, traces of robenidine were observed after 200 h. Five biotic transformation products of robenidine were discovered.     

Direct and indirect effects of metal contamination on soil biota in a Zn-Pb post-mining and smelting area (S Poland)

Effects of metal contamination on soil biota activity were investigated at 43 sites in 5 different habitats (defined by substratum and vegetation type) in a post-mining area. Sites were characterised in terms of soil pH and texture, nutrient status, total and exchangeable metal concentrations, as well as plant species richness and cover, abundances of enchytraeids, nematodes and tardigrades, and microbial respiration and biomass. The concentrations of total trace metals were highest in soils developed on mining waste (metal-rich dolomite), but these habitats were more attractive than sandy sites for plants and soil biota because of their higher content of organic matter, clay and nutrients. Soil mesofauna and microbes were strongly dependent on natural habitat properties. Pollution (exchangeable Zn and Cd) negatively affected only enchytraeid density; due to a positive relationship between enchytraeids and microbes it indirectly reduced microbial activity.