Effects of earthworm cast and powdered activated carbon on methane removal capacity of landfill cover soils

Landfill gases could be vented through a layer of landfill cover soil that could serve as a biofilter to oxidize methane to carbon dioxide and water. Properly managed landfill cover soil layers may reduce atmospheric CH4 emissions from landfills. In the present study, the effects of earthworm cast and powdered activated carbon (PAC) on the CH4 removal capacity of the landfill cover soil was investigated. For this purpose, column and batch tests were conducted using three different materials: typical landfill cover soil, landfill cover soil amended with earthworm cast, and landfill cover soil amended with PAC. The maximum CH4 removal rate of the columns filled with landfill cover soil amended with earthworm cast was 14.6mol m(-2)d(-1), whereas that of the columns filled with typical landfill cover soil was 7.4mol m(-2)d(-1). This result shows that amendment with earthworm cast could stimulate the CH4-oxidizing capacity of landfill cover soil. The CH4 removal rate of the columns filled with landfill cover soil amended with PAC also showed the same removal rate, but the vertical profile of gas concentrations in the columns and the methanotrophic population measured in the microbial assay suggested that the decrease of CH4 concentration in the columns is mainly due to sorption. Based on the results from this study, amendment of landfill cover soil with earthworm cast and PAC could improve its CH4 removal capacity and thus achieve a major reduction in atmospheric CH4 emission as compared with the same landfill cover soil without any amendment.     

Variation of zinc and copper in metallothionein-like protein in killifish (Oryzias latipes) exposed to cadmium

Killifish (Oryzias latipes) were exposed for 0, 24, 48 and 168 hours to cadmium solution. The hepatic cytoplasm was fractionated by using Sephadex G-75 and the content of zinc, copper and cadmium in the fractions was measured. Cadmium content in the metallothionein fraction increased with increase of exposure time. Zinc content in the metallothionein fraction was reduced at early exposure time and increased after prolonged exposure. Copper content in the metallothionein fraction was unchanged. It is shown that zinc bound to thionein in the liver is partially replaced by cadmium and that at least two isomers of metallothionein occur in this fish.     

Effects of copper fungicide residues on the microbial function of vineyard soils

The use of copper-based fungicides leads to an accumulation of copper (Cu) in vineyard soils, potentially causing adverse effects to the microbial function and fertility of the soil. This study used a soil microcosm approach to assess the effects of Cu accumulation on microbial function in vineyard soils. Surface soil samples were collected from 10 vineyards and a number of un-impacted reference sites in each of three different viticultural regions of Australia. The field-collected soils were transferred to microcosms and maintained for up to 93 days in the laboratory at 20–22 °C and 60 % of their maximum water-holding capacity. The microbial function of the soils was indicated by measuring phosphomonoesterase, arylsulfatase, urease, and phenol oxidase activities. In general, the vineyard soils had greater concentrations of Cu and lower enzyme activities than in the reference soils, although a weak negative relationship between Cu and enzyme activity could only be found for phosphomonoesterase activity. The results show that soil physical–chemical properties (i.e., organic carbon, pH) are greater determinants of soil enzyme activity than increased soil Cu concentration at the Cu concentrations present in vineyard soils.     

Heavy metal speciation and mobility assessment of arid soils in the vicinity of Al Ain landfill, United Arab Emirates

Sixty-four surface soil samples taken in the vicinity of Al Ain landfill were analysed for cadmium, chromium, copper, nickel, lead and zinc by inductively coupled plasma spectroscopy. Extraction techniques were used to establish the association of the total concentrations of the six metals in the soil samples with their contents in the exchangeable, carbonate, iron/manganese oxides, and residual fractions. In the investigated soils, the recorded concentrations were as follows: 0.043 mg kg^-1 for cadmium, 19.1 mg kg^-1 for chromium, 53.3 mg kg^-1 for copper, 60 mg kg^-1 for nickel, 13.7 mg kg^-1 for lead, and 117 mg kg^-1 for zinc. Cadmium, chromium, nickel, lead and zinc concentrations in the investigated soil samples reflect the natural background values in shale, whereas copper is slightly enriched. I-geo (geoaccumulation index) values of the metals in the soils under study indicate that they are uncontaminated with cadmium, chromium, nickel, lead and zinc, but contaminated to moderately contaminated with copper. Heavy metal contents in the sediments were found to be significantly influenced by different physico-chemical parameters. The effect of these parameters can be arranged in the following order: clay fraction > carbonate fraction > silt fraction > organic matter fractions. A sequential extraction procedure showed that the total concentrations of the heavy metals are largely bound to the residual phase (retained 71.4% of cadmium, 77.8% of chromium, 75% of copper, 47% of nickel, 62.8% of lead, and 75.8% of zinc). A likely sequence of mobility in the investigated soils is as follows: chromium > lead > nickel > cadmium > zinc > copper.     

The spatial distribution of eubacteria and archaea in sand-clay columns degrading carbon tetrachloride and methanol

The spatial distribution of microbial communities was investigated in anaerobic sand-clay columns fed methanol and carbon tetrachloride (CT). Microbial communities were characterized through analysis of soil samples with denaturing gradient gel electrophoresis (DGGE) and quantitative polymerase chain reaction (qPCR) for archaea and eubacteria. Increasing CT inlet concentrations to 29 microM lead to complete inhibition of methanol consumption in both columns. Although low levels of eubacteria and archaea were initially present in the clay soils in both columns, there was no significant microbial growth over 400 days in the clays beyond the interface with the sand zone. Thus, the potential for increased contaminant attenuation in heterogeneous sand-clay systems through biodegradation in the clay matrix zones may be limited in many systems.     

Biodegradation of trace gases in simulated landfill soil cover systems

The attenuation of methane and seven volatile organic compounds (VOCs) was investigated in a dynamic methane and oxygen counter gradient system simulating a landfill soil cover. The VOCs investigated were: Tetrachloromethane (TeCM), trichloromethane (TCM), dichloromethane (DCM), trichloroethylene (TCE), vinyl chloride (VC), benzene, and toluene. Soil was sampled at Skellingsted landfill, Denmark. The soil columns showed a high capacity for methane oxidation, with oxidation rates up to 184 g/m2/d corresponding to a 77% reduction of inlet methane. Maximal methane oxidation occurred at 15-20 cm depth, in the upper part of the column where there were overlapping gradients of methane and oxygen. All the chlorinated hydrocarbons were degraded in the active soil columns with removal efficiencies higher than 57%. Soil gas concentration profiles indicated that the removal of the fully chlorinated compound TeCM was because of anaerobic degradation, whereas the degradation of lower chlorinated compounds like VC and DCM was located in the upper oxic part of the column. Benzene and toluene were also removed in the active column. This study demonstrates the complexity of landfill soil cover systems and shows that both anaerobic and aerobic bacteria may play an important role in reducing the emission of trace components into the atmosphere.     

Biodegradation of Trace Gases in Simulated Landfill Soil

Abstract

The attenuation of methane and seven volatile organic compounds (VOCs) was investigated in a dynamic methane and oxygen counter gradient system simulating a landfill soil cover. The VOCs investigated were: Tetrachloromethane (TeCM), trichloromethane (TCM), dichloromethane (DCM), trichloroethylene (TCE), vinyl chlo-ride (VC), benzene, and toluene. Soil was sampled at Skellingsted landfill, Denmark. The soil columns showed a high capacity for methane oxidation, with oxidation rates up to 184 g/m²/d corresponding to a 77% reduction of inlet methane. Maximal methane oxidation occurred at 15–20 cm depth, in the upper part of the column where there were overlapping gradients of methane and oxygen. All the chlorinated hydrocarbons were degraded in the active soil columns with removal efficiencies higher than 57%. Soil gas concentration profiles indicated that the removal of the fully chlorinated compound TeCM was because of anaerobic degradation, whereas the degradation of lower chlorinated compounds like VC and DCM was located in the upper oxic part of the column. Benzene and toluene were also removed in the active column. This study demonstrates the complexity of landfill soil cover systems and shows that both anaerobic and aerobic bacteria may play an important role in reducing the emission of trace components into the atmosphere.     

Adsorption and desorption of Cu at high equilibrium concentrations by soil and clay samples from Bulgaria

Studies were carried out on the adsorption and desorption of added copper (from 100 to 600 microg g(-1)) to whole soils with contrasting properties: a Podzol (Godech A and Godech B) and a Chernozem (Gramada). Adsorption resulted in high Cu concentrations for the Podzol. The adsorbed copper, especially that in the B-horizon, is also potentially mobile, as judged by its ease of desorption on treatment with 0.01 m CaCl(2). A higher proportion of the added adsorbed copper is retained in Godech A soil (4% clay), than in Godech B soil (41% clay). Clay minerals are the principal adsorbent in the Podzol (Godech B), because of the high desorption observed at a low site coverage (7% CEC). The Godech B clay fraction (<0.001 mm) simulates the behaviour of the whole soil. The clay fraction from the Chernozem (Gramada) shows contrasting behaviour, as compared to the whole soil. Copper in the Chernozem is specifically (non-exchangeably) adsorbed, even at pH 2.7. A Langmuir model is appropriate for describing Cu-adsorption for the systems investigated at the acid pH values.     

Accumulation and mobility of zinc in soil amended with different levels of pig-manure compost

Applying manure compost not only results in zinc accumulation in the soil but also causes an increase in zinc mobility and enhances zinc leaching. In this study, the physical and chemical characteristics of zinc, zinc profiles, and zinc balance were investigated to characterise the fate of zinc in fields where the quality and amount of pig manure compost applied have been known for 13 years. Moreover, we determined zinc fractionation in both 0.1 mol L^?1HCl-soluble (mobile) and -insoluble (immobile) fractions. Adsorption of zinc in the soil was enhanced with increasing total carbon content following the application of pig manure compost. The 159.6 mg ha^?1 year^?1manure applied plot (triplicate) exceeded the Japanese regulatory level after only 6 years of applying pig manure compost, whereas the 53.2 mg ha^?1 year^?1 manure applied plot (standard) reached the regulatory level after 13 years. The zinc loads in the plots were 17.0 and 5.6 kg ha^?1 year^?1, respectively. However, 5.9 % and 17.2 % of the zinc loaded in the standard and the triplicate pig manure compost applied plots, respectively, were estimated to be lost from the plough layer. Based on the vertical distribution of mobile and immobile zinc content, a higher rate of applied manure compost caused an increase in the mobile zinc fraction to a depth of 40 cm. Although the adsorption capacity of zinc was enhanced following the application of pig manure compost, a greater amount of mobile zinc could move downward through the manure amended soil than through non manure-amended soil.     

Natural attenuation of diesel aliphatic hydrocarbons in contaminated agricultural soil

A diesel fuel spill at a concentration of 1 L m(-2) soil was simulated on a 12 m(2) plot of agricultural land, and natural attenuation of aliphatic hydrocarbons was monitored over a period of 400 days following the spill after which the aliphatic hydrocarbon concentrations were found to be below the legal contamination threshold for soil. The main fraction of these compounds (95%) remained at the surface layer (0-10 cm). Shortly after the spill (viz. between days 0 and 18), evaporation was the main origin of the dramatic decrease in pollutant concentrations in the soil. Thereafter, soil microorganisms used aliphatic hydrocarbons as sources of carbon and energy, as confirmed by the degradation ratios found. Soil quality indicators, soil microbial biomass and dehydrogenase activity, regained their original levels about 200 days after the spill.     

Microbial utilization and transformation of humic acid-like substances extracted from a mixture of municipal refuse and sewage sludge disposed of in a landfill

The purpose of the research was to establish whether humic acid-like substances (HA) related to municipal refuse disposed of in a landfill can resist microbial degradation and if they contribute, in that way, to long-term stabilization of landfill refuse. Using a mixture of 0.1 M Na(4)P(2)O(7) + 0.1 M NaOH, we extracted HA from municipal refuse mixed with sewage sludge and disposed of for up to 12 months, in a 40-m(3) model landfill. In laboratory experiments under aerobic conditions, up to 50% of HA was utilized as a supplementary source of nutrients by an assemblage of soil microorganisms in only 21 days. The microbial utilization was enhanced to over 80%, and up to 98%, respectively, if HA served as the sole source of carbon or nitrogen. Remaining HA which could be re-isolated from microbial cultures were lower in carbon (<12%) and nitrogen (<2.3%). Spectroscopic analysis (UV, Vis, FTIR) indicated losses, especially in aliphatic structural units, and a relative enhancement in aromatic structures. It was postulated that for their high degree of degradability, HA indigenous to that anthropogenic environment would not play an important role in the long-term stabilization of landfill refuse.     

Geochemical fractions of copper in soil chronosequences of selected European floodplains

The influence of soil formation on copper sorption is documented based on chronosequences of soils from three river floodplains in Europe (Danube, Ebro and Elbe). Sequential extraction was used to fractionate copper in original and spiked soils in order to study the long-term and short-term behaviour of copper retention. Copper partitioning among defined geochemical fractions was mainly determined by soil pH and the contents of carbonates, organic matter and Fe-/Mn-oxides and hydroxides. Copper extracted with NH(2)OH.HCl correlated well with the contents of crystalline Fe-oxides and hydroxides, demonstrating increasing retention capacity with progressing soil development. Copper retained in original soils was found in more strongly bound fractions, whereas sorption of freshly added copper was primarily influenced by the presence of carbonates. Beyond the effect of progressing soil formation, variations in organic carbon contents due to different land use history affected the copper retention capacity of the investigated soils.     

Biological activity in metal-contaminated calcareous agricultural soils: the role of the organic matter composition and the particle size distribution

Organic matter (OM) plays a key role in microbial response to soil metal contamination, yet little is known about how the composition of the OM affects this response in Mediterranean calcareous agricultural soils. A set of Mediterranean soils, with different contents and compositions of OM and carbonate and fine mineral fractions, was spiked with a mixture of Cd, Cu, Pb, and Zn and incubated for 12 months for aging. Microbial (Biolog Ecoplates) and enzyme activities (dehydrogenase, DHA; β-galactosidase, BGAL; phosphatase, PHOS; and urease, URE) were assessed and related to metal availability and soil physicochemical parameters. All enzyme activities decreased significantly with metal contamination: 36–68 % (DHA), 24–85 % (BGAL), 22–72 % (PHOS), and 14–84 % (URE) inhibitions. Similarly, catabolic activity was negatively affected, especially phenol catabolism (～86 % compared to 25–55 % inhibition for the rest of the substrates). Catabolic and DHA activities were negatively correlated with ethylenediaminetetraacetic acid (EDTA)-extractable Cd and Pb, but positively with CaCl₂, NaNO₃, and DTPA-extractable Cu and Zn. Soluble OM (water- and hot-water-soluble organic C) was positively related to enzyme and catabolic activities. Recalcitrant OM and fine mineral fractions were positively related to BGAL and PHOS. Conversely, catabolic activity was negatively related to clay and positively to silt and labile OM. Results indicate that the microbial response to metal contamination is highly affected by texture and OM composition.     

Enhanced in situ bioremediation of phenol in bioestimulated unsaturated and saturated sand-bed columns.

Biodegradation of phenol was observed in unsaturated sandbed columns, in which phenol concentration declined from 298 mg phenol/kg sand to less than 1 mg/kg after 21 days. In saturated sand-bed columns, phenol concentration declined from 230 mg phenol/kg to less than 1 mg/kg after 37 days. Pseudo-first-order phenol biodegradation rates were in the range 0.25 days(-1) (R2 = 0.9) to 0.66 days(-1) (R2 = 0.85) and 0.08 days(-1) (R2 = 0.68) to 0.14 days(-1) (R2 = 0.84) in the unsaturated and saturated sand-bed columns, respectively. Unsaturated columns presented a higher biomass density (21.5 mg/g) in the sand-bed and lower biomass concentration in the aqueous phase (3.5 NTU) compared with the saturated columns (6.4 mg/g and 14.0 NTU). A high concentration of phenol releases in the sand-bed columns resulted in an initial inhibition of microbial activity and destabilization of the attached biomass.     

Changes in soil organic matter chemical properties after organic amendments

Organic inputs are used to improve soil physical and chemical properties, but the corresponding changes in soil organic matter (SOM) chemical properties are not well known. In this study, we compared some characteristics of the SOM of a soil receiving either no organic inputs, or two different amendments during 15 years (straw or conifer compost). Quantities of organic carbon and C/N values were determined on particle size fractions after physical soil fractionation to localize changes due to amendments. Contents in reactive functional groups, acid-base properties and copper binding affinities were determined by titration experiments for the soluble fraction of SOM: the fulvic acid fraction (FA). Data of FA extracted from the bulk soil were compared to data of FA extracted from the <20 microm size fraction with the help of either a discrete or a continuous model (fit of data with FITEQL or NICA, respectively). Copper binding characteristics of FA extracted from the <20 microm size fraction did not change significantly after organic inputs, while those of FA extracted from the bulk organic-amended soils were found different from the ones with no amendment. Minor effects observed in the finer soil fractions were ascribed to their low turn-over of organic carbon and/or to a greater homogeneity in the nature of the organic carbon entering these fractions. Our results show major chemical changes in coarser soil organic fractions after organic amendments.     

Interspecific variation in heavy metal body concentrations in Hong Kong marine invertebrates

Accumulated body concentrations of cadmium, copper and zinc were investigated in 19 species of intertidal invertebrates (the barnacles Tetraclita squamosa, Capitulum mitella, Balanus amphitrite, Megabalanus volcano, the bivalves Saccostrea cucullata, Septifer virgatus and Brachidontes atratus, the chiton Acanthopleura japonica and the gastropods Cellana grata, Cellana toreuma, Patelloida saccharina, Patelloida pygmaea, Siphonaria japonica, Tegula argyrostoma, Lunella coronata, Monodonta labio, Nerita albicilla, Thais clavigera and Thais luteostoma) collected from a relatively unpolluted area in Hong Kong, i.e. two shores within the Cape d'Aguilar Marine Reserve. In general body metal concentrations could be explained by the accumulation strategy of the analysed organism and by physiological requirements for the essential metals, i.e. copper and zinc. Zinc concentrations were, therefore, greatest in the barnacles and the oyster S. cucullata. Copper concentrations were greatest in those gastropods containing the respiratory pigment haemocyanin and in S. cucullata. One species collected from the sheltered shore, i.e. T. luteostoma, had much higher copper body concentrations compared with exposed shore conspecifics and this may be attributed to a diet that was dominated by oysters, which have high copper body concentrations. In contrast to both copper and zinc, cadmium body concentrations showed little interspecific variation.     

Preliminary evidence that copper inhibits the degradation of DDT to DDE in pip and stonefruit orchard soils in the Auckland region,New Zealand

Orchards (n=13) were sampled as part of a larger survey investigating agrichemical residues (pesticides and trace elements) in cropping soils in the Auckland region, New Zealand. SigmaDDT concentrations in orchard soils ranged from <0.03 to 24.41 mg kg(-1). DDT (o,p'- and p,p'-) comprised at least 40% of the SigmaDDT residues in 67% of orchards in which DDT residues were detected. There was a highly significant negative correlation (-0.924, P<0.001) between copper concentration (21-490 mg kg-1) and the ratio of DDE:DDT (0.4-5.2) in pip and stonefruit orchard soils. In further investigations involving five pip and stone fruit orchard sites and one grazing paddock it was found that soil respiration and the ratio of soil microbial carbon to soil carbon (%Cmic/Org-C) in orchard soils decreased with increasing copper concentration. These findings are consistent with the conclusion that elevated soil copper concentrations in pip and stone fruit orchard soils in the Auckland region may have reduced the ability of the indigenous soil microbial community to degrade DDT to DDE     

Changes of copper speciation in maize rhizosphere soil

Chemical forms of copper in the rhizosphere and bulk soil of maize were investigated using rhizobox cultivation and sequential extraction techniques. The copper accumulations were also determined. The results demonstrated that there were continuous changes in copper fractionation within the maize rhizosphere. Initially, the amount of exchangeable copper increased before dropping below the initial level after 40 days or so. Carbonate associated copper followed a similar trend of change, but with a slower pace than the exchangeable copper. The increase in carbonate associated copper only become evident after 30 days, with the net loss occurring after 60 days. There were also initial increases in oxide bound copper as well as decreases in the organic matter associated copper, both followed by a turnover after 40-50 days. The accumulation of copper in the maize plant was found to be biomass dependent. The amount of accumulated copper absorbed in the plant material exceeded the initial quantity of the exchangeable copper in the soil, revealing a transformation from less bioavailable to more bioavailable fractions. During cultivation, decreases in redox potential and increases in pH, dissolved organic carbon (DOC), and microbial activity in the maize rhizosphere were observed. The change in copper speciation may result from root-induced changes in DOC, redox potential, and microbial activity in the rhizosphere.     

Copper activity in soil solutions of calcareous soils

Copper partitioning was studied in seven calcareous soils at moisture content corresponding to 1.2 times the field moisture content (soil water potential 7.84 J kg(-1)). Copper retention was accompanied by the release in soil solution of Ca(2+), Mg(2+), Na(+), and H(+), and the total amount of these cations released was 0.8 to 1.09 times the amount of Cu sorbed (mol(c):mol(c)). The relationships between Cu activity and pH, and the balance of cations in soils correspond with the surface precipitation of CuCO(3) as the main mechanism of Cu retention. The values of ion activity product of surface precipitate were close for all studied soils with the average log(IAP(CuCO(3)))=-15.51. The relationship between copper activity in soil solutions and soil properties is well fit by a regression relating pCu (-log copper ion activity) with soil pH, total Cu, and carbonate content.     

猪粪堆肥中铜锌与腐殖质组分的结合竞争

为研究猪粪堆肥中铜锌与腐殖质组分的结合竞争,以猪粪和秸秆为堆腐原料,进行了为期36 d的好氧堆肥实验,研究猪粪堆肥过程中腐殖质组分(胡敏酸和富里酸)、胡敏酸结合态铜锌、富里酸结合态铜锌含量的变化。结果表明,堆肥结束后,腐殖化程度提高,胡敏酸碳含量增加394.4%,富里酸碳含量降低64.9%,腐殖化指数从0.24增加到3.33;随着堆肥的进行,胡敏酸结合态铜锌含量分别增加394.3%和56%,而富里酸结合态铜锌含量分别下降17.5%和28.4%;相关分析表明,胡敏酸结合态铜、富里酸结合态锌与胡敏酸、富里酸碳含量及腐殖化指数均成显著相关(P<0.01);堆肥过程中,胡敏酸结合态铜与富里酸结合态铜之比大于1,而胡敏酸结合态锌与富里酸结合态锌小于1,另外,胡敏酸中的Cu/Zn大于1,而富里酸中的Cu/Zn小于1,表明在腐殖质中铜主要与胡敏酸结合,而锌主要与富里酸结合。研究揭示了猪粪堆肥中重金属铜锌与不同腐殖质组分的结合竞争关系,为畜禽粪便堆肥土地利用的风险评估和风险控制提供科学依据。