Fluxes and pools of methane in wetland rice soils with varying organic inputs

Measurements of methane emission rates and concentrations in the soil were made during four growing seasons at the International Rice Research Institute in the Philippines, on plots receiving different levels of organic input. Fluxes were measured using the automated closed chambers system (total emission) and small chambers installed between plants (water surface flux). Concentrations of methane in the soil were measured by collecting soil cores including the gas phase (soil-entrapped methane) and by sampling soil solution in situ (dissolved methane). There was much variability between seasons, but total fluxes from plots receiving high organic inputs (16–24 g CH₄ m^–2) always exceeded those from the low input plots (3–9 g CH₄ m^–2). The fraction of the total emission emerging from the surface water (presumably dominated by ebullition) was greater during the first part of the season, and greater from the high organic input plots (35–62%) than from the low input plots (15–23%). Concentrations of dissolved and entrapped methane in the low organic input plots increased gradually throughout the season; in the high input plots there was an early-season peak which was also seen in emissions. On both treatments, periods of high methane concentrations in the soil coincided with high rates of water surface flux whereas low concentrations of methane were generally associated with low flux rates.     

Fluroxypyr biodegradation in soils by multiple factors

Fluroxypyr (4-amino-3,5-dichloro-6-fluoro-2-pyridinyl-1-methylheptyl ester) is a widely used herbicide for controlling weeds, fungi, and insects. However, extensive use of the herbicide has led to its high accumulation in ecosystems and contamination to soils and crops. Environmental behaviors and fate of herbicides are dependent on many physiochemical and biological factors. Whether fluroxypyr is significantly affected and how it is degraded under the environmental conditions is largely unknown. The present study investigated the effects of soil microbe, soil type, dissolved organic matter (DOM), temperature, soil moisture, and surfactant on fluroxypyr degradation in soils. Application of DOM derived from sludge and straw to fluroxypyr-contaminated soils increased degradation of fluroxypyr. Environmental factors such as temperature, moisture, soil microbe and soil type could affect the rate of fluroxypyr dissipation. Also, the microorganism affected the degradation of fluroxypyr. Analysis by gas chromatography-mass revealed that the reaction in soils might include the removal of 1-methylheptyl ester to generate fluroxypyr acid (4-amino-3,5-dichloro-6-fluoro-2-pyridiny). Our results provided initial data that a set of biological and physiochemical factors coordinately regulates the decay of fluroxypyr in soils.     

Measuring and modeling ammonium adsorption by calcareous soils

The aim of this study was assessment of ammonium (NH ₄ ⁺ ) adsorption isotherms in some agricultural calcareous soils and modeling of that by using the mechanistic exchange model. Ten surface soils (0–30 cm) were collected from areas covered with different land uses in Hamedan, western Iran. Isotherm experiments were carried out by concentrations of NH ₄ ⁺ prepared from NH₄Cl salt (0, 10, 20, 30, 40, 50, 100, and 150 mg NH ₄ ⁺ ?l^?1) in presence of 0.01 M CaCl₂ solution. The empirical models including simple adsorption isotherm and Freundlich equations were fitted well to the experimental data. The average amounts of adsorbed NH ₄ ⁺ in studied soils varied from 8.95 to 35.23 %. Adsorption percentage indicated positive correlation with pH, cation-exchange capacity (CEC), equivalent calcium carbonate, and clay content and had negative correlation with sand content. In order to predict and model NH ₄ ⁺ adsorption, cation-exchange model in PHREEQC program was used. The model could simulate the NH ₄ ⁺ adsorption very well in all studied soils. The values of CEC played the major role in modeling of NH ₄ ⁺ adsorption in this study indicating that cation-exchange process was the major mechanism controlling NH ₄ ⁺ adsorption in studied soils.     

Restoration of properties of cultivated soils polluted by copper and nickel

The long-term observations of the restoration of chemical and biological properties of cultivated podzol soil polluted by airborne emissions from a copper-nickel smelter located in the western Arctic of Russia were carried out. After 8 years, the total content of copper in soil decreased to a third (from 6230 to 2080 mg kg(-1)) and nickel to a sixth (from 3500 to 580 mg kg(-1)). Based on these observations, the removal time for heavy metals to reach permissible levels was calculated. The estimate was 100 years for copper and 108 years for nickel. Soil remained toxic to wheat seedlings, especially to their roots, for the whole observation period. A restoration of the number and activity of soil microorganisms was associated with the reduction in soil metal-toxicity. The number of non-sporeforming saprophytic bacteria was quickly restored concurrently with the removal of metals from the soil; fungal biomass also increased.     

Estimates of animal methane emissions

The enteric methane emissions into the atmospheric annually from domestic animals total about 77 Tg. Another 10 to 14 Tg are likely released from animal manure disposal systems. About 95% of global animal enteric methane is from ruminants, a consequence of their large populations, body size and appetites combined with the extensive degree of anaerobic microbial fermentation occurring in their gut. Accurate methane estimates are particularly sensitive to cattle and buffalo census numbers and estimated diet consumption. Since consumption is largely unknown and must be predicted, accuracy is limited often by the information required, i.e., distribution of animals by class, weight and productivity. Fraction of the diet lost as enteric methane mostly falls into the range of 5.5–6.5% of gross energy intake for the world's cattle, sheep and goats. Manure methane emissions are heavily influenced by fraction of disposal by anaerobic lagoon. Non-ruminants, i.e., swine, become major contributors to these emissions.     

Risk assessment of soils contaminated by mercury mining, Northern Spain

Analytical results of soil samples taken in three different mercury mining sites in Northern Spain are studied to assess the potential adverse health effects of the exposure to trace elements associated with the mining process. Doses contacted through ingestion and inhalation and the dose absorbed through the skin were calculated using USEPA's exposure parameters and the US Department of Energy's toxicity values. The results of the risk assessment indicate that the highest risk is associated with ingestion of soil particles and that the trace element of major concern is arsenic, the exposure to which results in a high cancer risk value for all the sites ranging from 3.3 × 10(-5) to 3.6 × 10(-3), well above the 1 × 10(-5) probability level deemed unacceptable by most regulatory agencies. Regarding non-cancer effects, exposure to polluted soils yields an aggregate hazard index above the threshold value of 1 for all three sites, with As and Hg as the main contributors. Risk assessment has proven to be a very useful tool to identify the contaminants and exposure pathways of most concern in the soils from metal mining sites, as well as to categorize them in terms of action priority to ensure fitness for use.     

Assessment of phenanthrene bioavailability in aged and unaged soils by mild extraction

It has become apparent that the threat of an organic pollutant in soil is directly related to its bioavailable fraction and that the use of total contaminant concentrations as a measure of potential contaminant exposure to plants or soil organisms is inappropriate. In light of this, non-exhaustive extraction techniques are being investigated to assess their appropriateness in determining bioavailability. To find a suitable and rapid extraction method to predict phenanthrene bioavailability, multiple extraction techniques (i.e., mild hydroxypropyl-β-cyclodextrin (HPCD) and organic solvents extraction) were investigated in soil spiked to a range of phenanthrene levels (i.e., 1.12, 8.52, 73, 136, and 335 μg g^− 1 dry soil). The bioaccumulation of phenanthrene in earthworm (Eisenia fetida) was used as the reference system for bioavailability. Correlation results for phenanthrene suggested that mild HPCD extraction was a better method to predict bioavailability of phenanthrene in soil compared with organic solvents extraction. Aged (i.e., 150 days) and fresh (i.e., 0 day) soil samples were used to evaluate the extraction efficiency and the effect of soil contact time on the availability of phenanthrene. The percentage of phenanthrene accumulated by earthworms and percent recoveries by mild extractants changed significantly with aging time. Thus, aging significantly reduced the earthworm uptake and chemical extractability of phenanthrene. In general, among organic extractants, methanol showed recoveries comparable to those of mild HPCD for both aged and unaged soil matrices. Hence, this extractant can be suitable after HPCD to evaluate risk of contaminated soils.     

Uptake of arsenic by alkaline soils near alkaline coal fly ash disposal facilities

The attenuation of arsenic in groundwater near alkaline coal fly ash disposal facilities was evaluated by determining the uptake of arsenic from ash leachates by surrounding alkaline soils. Ten different alkaline soils near a retired coal fly ash impoundment were used in this study with pH ranging from 7.6 to 9.0, while representative coal fly ash samples from two different locations in the coal fly ash impoundment were used to produce two alkaline ash leachates with pH 7.4 and 8.2. The arsenic found in the ash leachates was present as arsenate [As(V)]. Adsorption isotherm experiments were carried out to determine the adsorption parameters required for predicting the uptake of arsenic from the ash leachates. For all soils and leachates, the adsorption of arsenic followed the Langmuir and Freundlich equations, indicative of the favorable adsorption of arsenic from leachates onto all soils. The uptake of arsenic was evaluated as a function of ash leachate characteristics and the soil components. The uptake of arsenic from alkaline ash leachates, which occurred mainly as calcium hydrogen arsenate, increased with increasing clay fraction of soil and with increasing soil organic matter of the alkaline soils. Appreciable uptake of arsenic from alkaline ash leachates with different pH and arsenic concentration was observed for the alkaline soils, thus attenuating the contamination of groundwater downstream of the retired coal fly ash impoundment.     

Dissolved methane in Indian freshwater reservoirs

Emission of methane (CH₄), a potent greenhouse gas, from tropical reservoirs is of interest because such reservoirs experience conducive conditions for CH₄ production through anaerobic microbial activities. It has been suggested that Indian reservoirs have the potential to emit as much as 33.5 MT of CH₄ per annum to the atmosphere. However, this estimate is based on assumptions rather than actual measurements. We present here the first data on dissolved CH₄ concentrations from eight freshwater reservoirs in India, most of which experience seasonal anaerobic conditions and CH₄ buildup in the hypolimnia. However, strong stratification prevents the CH₄-rich subsurface layers to ventilate CH₄ directly to the atmosphere, and surface water CH₄ concentrations in these reservoirs are generally quite low (0.0028–0.305 μM). Moreover, only in two small reservoirs substantial CH₄ accumulation occurred at depths shallower than the level where water is used for power generation and irrigation, and in the only case where measurements were made in the outflowing water, CH₄ concentrations were quite low. In conjunction with short periods of CH₄ accumulation and generally lower concentrations than previously assumed, our study implies that CH₄ emission from Indian reservoirs has been greatly overestimated.     

Soil pollution by PAHs in urban soils: a comparison of three European cities

The purpose of this study was to determine the degree of contamination with polycyclic aromatic hydrocarbons (PAHs) in samples of urban soil from three European cities: Glasgow (UK), Torino (Italy) and Ljubljana (Slovenia). Fifteen PAHs (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, indeno[1,2,3-c,d]pyrene) were measured in urban soil samples, using harmonised sampling, sample extraction and analyte quantification methods. Although the mean concentration of each PAH in urban soils of each city showed a wide range of values, high levels of contamination were only evident in Glasgow, where the sum of concentrations of 15 PAHs was in the range 1487-51,822 microg kg(-1), cf. ranges in the other two cities were about ten-fold lower (89.5-4488 microg kg(-1)). The three predominant PAHs were phenanthrene, fluoranthene and pyrene, with the sum of these compounds about 40% of the total PAH content. These data, together with some special molecular indices based on ratios of selected PAHs, suggest pyrogenic origins, especially motor vehicle exhausts, to be the major sources of PAHs in urban soils of the three cities. The largest concentrations for PAHs were often found in sites close to the historic quarters of the cities. Overall, the different climatic conditions, the organic carbon contents of soil, and the source apportionment were the dominant factors affecting accumulation of PAHs in soil.     

甲烷气体标准样品的研制

对称量制备甲烷气体标准样品的制备方法进行了详细研究 ,对可能引起甲烷量值不确定度的各种误差来源进行了分析。文中提出的甲烷气体标准样品制备方法具有很好的重现性 ,所制备的甲烷气体标准样品具有良好的压力稳定性并已能在三种气瓶中稳定保存 1 8个月 ,其量值准确、可比 ,并已在全国环境监测网试用。     

Status of heavy metals in agricultural soils as affected by different patterns of land use

This study was conducted to determine status of heavy metals in agricultural soils under different patterns of land use. A total of 38, 40 and 45 soil samples for bare vegetable field, greenhouse vegetable field, and grain crop field were respectively taken from surface layer (0–20 cm) from selected experimental areas away from suburbs of ten counties (or districts or cities) in four provinces or municipalities of Huabei plain in north China. Information of crop production history, including varieties, rotation systems and fertilizer use, at the corresponding sampling sites was surveyed. Soil total Cu, Zn, Cd, Pb, Cr, As and Hg were measured. The results showed that the contents of total Cu, Zn, Cd, Pb, Cr, As, and Hg in the soil samples, especially soil total Cu and Zn contents, were higher in the bare vegetable field and the greenhouse vegetable field than that in the grain crop field. Long-term use of excessive chemical fertilizers and organic manures in the bare vegetable field and the greenhouse vegetable field contributed to the accumulation of Cu, Zn, and other heavy metals in the soils. The contents of total Cu, Zn, and other heavy metals in soils increased with increasing vegetable production history of the research areas. In comparison with the grain crop field, the comprehensive pollution indices of the seven soil heavy metals and the single-factor pollution indices of soil Zn, Cu, Cd, Cr, and Hg based on the second criterion of Environmental Quality Standard for Soils were significantly higher in the bare vegetable field and the greenhouse vegetable field. Soils from the greenhouse vegetable field were slightly contaminated according to the comprehensive pollution index, and soils from the bare vegetable field and the grain crop field were at the warning heavy metal pollution level. The soils were contaminated with Cd according to the single-factor pollution index. The Cd pollution was relatively more serious in the bare vegetable field and the greenhouse vegetable field than that in the grain crop field. The soils selected with different land use patterns were not contaminated with Zn, Cu, Pb, Cr, As and Hg.     

Mercury emission and dispersion models from soils contaminated by cinnabar mining and metallurgy

The laboratory flux measurement system (LFMS) and dispersion models were used to investigate the kinetics of mercury emission flux (MEF) from contaminated soils. Representative soil samples with respect to total Hg concentration (26-9770 μg g(-1)) surrounding a decommissioned mercury-mining area (Las Cuevas Mine), and a former mercury smelter (Cerco Metalúrgico de Almadenejos), in the Almadén mercury mining district (South Central Spain), were collected. Altogether, 14 samples were analyzed to determine the variation in mercury emission flux (MEF) versus distance from the sources, regulating two major environmental parameters comprising soil temperature and solar radiation. In addition, the fraction of the water-soluble mercury in these samples was determined in order to assess how MEF from soil is related to the mercury in the aqueous soil phase. Measured MEFs ranged from less than 140 to over 10,000 ng m(-2) h(-1), with the highest emissions from contaminated soils adjacent to point sources. A significant decrease of MEF was then observed with increasing distance from these sites. Strong positive effects of both temperature and solar radiation on MEF was observed. Moreover, MEF was found to occur more easily in soils with higher proportions of soluble mercury compared to soils where cinnabar prevails. Based on the calculated Hg emission rates and with the support of geographical information system (GIS) tools and ISC AERMOD software, dispersion models for atmospheric mercury were implemented. In this way, the gaseous mercury plume generated by the soil-originated emissions at different seasons was modeled. Modeling efforts revealed that much higher emissions and larger mercury plumes are generated in dry and warm periods (summer), while the plume is smaller and associated with lower concentrations of atmospheric mercury during colder periods with higher wind activity (fall). Based on the calculated emissions and the model implementation, yearly emissions from the "Cerco Metalúrgico de Almadenejos" decommissioned metallurgical precinct were estimated at 16.4 kg Hg y(-1), with significant differences between seasons.     

Metabolic and bacterial diversity in soils historically contaminated by heavy metals and hydrocarbons

The aim of this study was to characterize soils contaminated by different levels of heavy metals and hydrocarbons (Madonna Dell'Acqua, Pisa, Italy). The soils were chemically and biochemically analysed by measuring the standard chemical properties and some enzyme activities related to microbial activity (dehydrogenase activity) and the soil carbon cycle (total and extracellular beta-glucosidase activities). The metabolic capacities of soil microorganisms to degrade hydrocarbons through catechol 2,3-dioxygenase were also described. The microbial diversity of contaminated and uncontaminated soils was estimated by denaturing gradient gel electrophoresis (DGGE) of amplified 16S rDNA sequences. The PCR/single-strand conformation polymorphism (PCR/SSCP) method was used to estimate the genetic diversity of PAH-degrading genes in both contaminated and uncontaminated soils. A greater bacterial diversity and lower catechol 2,3-dioxygenase activity was detected in unpolluted soils. The complexity of the microbial community (Shannon and Simpson indices) as well as the dehydrogenase soil activity negatively correlated with contamination levels. The greatest PAH-degrading gene diversity and the most intense catechol 2,3-dioxygenase activity were found in the soils with the highest levels of hydrocarbons. Heavy metals and hydrocarbon pollution has caused a genetic and metabolic alteration in microbial communities, corresponding to a reduction in microbial activity. A multi-technique approach combining traditional biochemical methods with molecular-based techniques, along with some methodological improvements, may represent an important tool to expand our knowledge of the role of microbial diversity in contaminated soil.     

The levels and composition of persistent organic pollutants in alluvial agriculture soils affected by flooding

The concentrations and composition of persistent organic pollutants (POPs) were determined in alluvial soils subjected to heavy flooding in a rural region of Poland. Soil samples (n?=?30) were collected from the upper soil layer from a 70-km² area. Chemical determinations included basic physicochemical properties and the contents of polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and polycyclic aromatic hydrocarbons (PAHs, 16 compounds). The median concentrations of Σ7PCB (PCB28?+?PCB52?+?PCB101?+?PCB118?+?PCB138?+?PCB153?+?PCB180), Σ3HCH (α-HCH?+?β-HCH?+?γ-HCH) and Σ3pp′(DDT?+?DDE?+?DDD) were 1.60?±?1.03, 0.22?±?0.13 and 25.18?±?82.70 μg kg^?1, respectively. The median concentrations of the most abundant PAHs, phenanthrene, fluoranthene, pyrene, benzo[b]fluoranthene and benzo[a]pyrene were 50?±?37, 38?±?27, 29?±?30, 45?±?36 and 24?±?22 μg kg^?1, respectively. Compared with elsewhere in the world, the overall level of contamination with POPs was low and similar to the levels in agricultural soils from neighbouring countries, except for benzo[a]pyrene and DDT. There was no evidence that flooding affected the levels of POPs in the studied soils. The patterns observed for PAHs and PCBs indicate that atmospheric deposition is the most important long-term source of these contaminants. DDTs were the dominant organochlorine pesticides (up to 99 %), and the contribution of the parent pp′ isomer was up to 50 % of the ΣDDT, which indicates the advantage of aged contamination. A high pp′DDE/pp′DDD ratio suggests the prevalence of aerobic transformations of parent DDT. Dominance of the γ isomer in the HCHs implies historical use of lindane in the area. The effect of soil properties on the POP concentrations was rather weak, although statistically significant links with the content of the <0.02-mm fraction, C_total or N_total were observed for some individual compounds in the PCB group.     

Measurement of total antimony and antimony species in mine contaminated soils by ICPMS and HPLC-ICPMS

This paper describes the measurement of total antimony and antimony species in "real world" mine contaminated sediments using ICPMS and HPLC-ICPMS. Low and high temperature microwave extraction procedures (90 degrees C and 150 degrees C, respectively) using a range of nitric-hydrochloric acid combinations were examined as to their efficacy to extract antimony from six mine contaminated soils and a certified reference material. The use of the higher temperature with nitric-hydrochloric acid (1:2 (v/v)) was suitable to release antimony from sediments and the certified reference material, NIST 2710 Montana soil. Antimony concentrations obtained using this acid mixture were similar to those obtained using a more aggressive extraction with nitric, hydrochloric, perchloric and hydrofluoric acid mixture. A 25 mM citric acid solution at 90 degrees C for 15 min extracted 47-78% of antimony from soils. A Hamilton PRP X-100 anion exchange column with 20 mM EDTA mobile phase, pH 4.5, flow rate 1.5 mL min(-1) and column temperature of 50 degrees C was used to separate antimony species. Column recoveries ranged from 78-104%. The predominant form of antimony was Sb(5+). Little conversion of Sb(5+) occurred (<5%) during extraction, however, significant conversion of Sb(3+) occurred (approximately 36%). The extraction of antimony species with citric acid should be useful in the determination of inorganic antimony available to plants, as plants commonly excrete carboxylic acids, including citric acid, into their rhizospheres to mobilise trace elements for nutritional purposes.     

Methane fluxes in aerobic soils

Aerobic soils are an important sink for methane (CH₄), contributing up to 15% of global CH₄ destruction. However, the sink strength is significantly affected by land management, nitrogen (N) fertilizers and acidity. The rates of uptake from the atmosphere of both enhanced (10 ppmv) and ambient (2 ppmv) concentrations of CH₄ were measured in laboratory incubations of soil cores under controlled conditions taken from sites in the U.K. and Germany. The most rapid rates of uptake were measured in soil from deciduous woodland at pH 4 (measured in water). Extended (150 years) cultivation of land for arable crops reduced uptake rate by 85% compared to that in the same soil under an adjacent woodland. The long-term application of ammonium (NH₄)-based fertilizer, but not nitrate (NO₃)-based fertilizer, completely inhibited CH₄ uptake, but the application for the same period of farmyard manure (FYM) that contained more N than the fertilizer had no inhibitory effect. Where a combination of FYM and inorganic fertilizer was applied there was a reduction in methane uptake rate compared to plots receiving solely FYM.Autoclaving showed that the uptake of CH₄ was microbially mediated. The most likely causes of the inhibitory effects seen are (i) insufficient concentrations of CH₄ in situ to activate methane monooxygenase; (ii) the direct inhibition of CH₄ oxidation by NH _inf4 ^sup+ ions; (iii) the suppression of methanotrophs by NH₄-based fertilizers; (iv) the requirement of methanotrophs for a stable soil architecture which is incompatible with the disturbance caused by regular arable cultivation.