Hydrocarbon Uptake by Roots of Vicia faba (Fabaceae)

Vicia faba was grown in crude oil polluted soil and its roots were extracted for the detection and estimation of hydrocarbons. Saturated and unsaturated Aliphatic Hydrocarbons (AHs) ranging from C₂₂ to C₃₆ were identified in AHs fraction. However, PAHs were not present in the same extract. This could be due to the fact that PAHs being toxic compounds are not accumulated in the plant root extracts of V. faba grown in crude oil polluted soil. Three phytoalexins were identified and estimated by mass spectrometric analysis in the root extracts of V. faba. These three compounds are 2-t-butyl-4-(dimethyl benzyl) phenol, 2, 4-bis (dimethyl benzyl) phenol and 2,4-bis (dimethyl benzyl)-6-butyl phenol. These phenolics in V. faba are being reported for the first time. These compounds are presumably elicited as a direct stress on crude oil hydrocarbons on the roots of this plant.     

Induction of cytochrome P4501A and endocrine disrupting effects of school incinerator residues

The emission of the dioxin-like compounds from on-site waste incinerators of seven schools in Kyonggi Province of Korea was evaluated by determination of the cytochrome P4501A(CYP1A) catalytic activity and antiestrogenic activity using cell culturemicrobioassay. The residue samples were extracted in a Soxhlet apparatus using toluene for 20 hr. The concentrated crude extractswere fractionated with a basic alumina column. Dioxin-like compounds were then extracted. Induction of CYP1A activity in a rat(H4IIE) hepatoma cell line was used as indicator of biologicaleffect of incinerator residues and measured as 7-ethoxyresorufin-O-deethylase(EROD) activities. The EROD activities of fraction II extracts (one of the two extracts) in the H4IIE cells were from 0.044±0.002 to 4.424±0.351 ng-TEQ g^-1 (TCDD Toxicity equivalent), showing relatively high inducing capacity. Antisetrogenicity of the extracts was measured as decrease in E₂-induced cell proliferation. Most of the extracts showed antiestrogenic activity in MCF7-BUS cell.The TEQ levels of the incinerator residues and the antiestrogenicactivities were in good correlation, strongly suggesting that thepotent toxic emissions were indeed produced from the on-site school waste semi-incinerators and could cause the antiestrogenicity.     

Aliphatic and polycyclic aromatic hydrocarbons in sediments of Kaohsiung Harbour and adjacent coast, Taiwan

Surficial sediment samples collected from Kaohsiung Harbour and its nearby coast were analyzed for aliphatic hydrocarbons and parent polycyclic aromatic hydrocarbons (PAHs). According to our results, the average total concentrations of n-alkanes (n-C₁₂ to C₃₅) and aromatics (15 PAHs) were 4.33 µg g^–1 dry weight (ranged 0.46–22.60) and 0.59 µg g^–1 dry weight (ranged 0.09–1.75), respectively. The highest concentrations of aliphatic and aromatic hydrocarbons were recorded in stations near the estuaries of Qianzhen River and Love River, respectively. Aliphatic hydrocarbons in the samples indicate that there has been significant non-petrogenic, possibly terrestrial, contribution in the sediment of the open coast of Kaohsiung Harbour and that there has been dominant contribution from petrogenic sources in the sediment of the inner harbour. PAHs, detected in the samples, however, indicated a higher pyrolytic contribution in open-coast samples and a higher petrogenic contribution in the inner harbour. Overall, sediment concentrations of total alkanes in this study were comparable to those found in Victoria Harbour, Hong Kong and are higher than those found in Xiamen Harbour, China. Concentrations of total PAHs in inner Kaohsiung Harbour sediments were relatively lower than those found in Victoria Harbour, Hong Kong and Xiamen Harbour, China, but comparable to those found in Hsin-ta Harbour, Taiwan and Incheon Harbour, Korea. In comparison with several effect-based sediment quality guidelines, most PAH concentrations found in samples taken from inner harbour stations exceeded the Threshold Effect Level of Florida indicating a slight possibility of adverse effects.     

Characterization of hydrocarbon contaminated areas by multivariate statistical analysis: Case studies

Analysis of soil gases is a relatively rapid and inexpensive method to delineate and measure hydrocarbon contamination in the subsurface caused by diesel or gasoline. Techniques originally developed for petroleum exploration have been adapted to tracking hydrocarbons which have leaked or spilled at or below the earth's surface.Discriminant analysis (a multivariate statistical technique) is used to classify soil gas samples of C₁ to C₇ hydrocarbons as biogenic (natural soil gases) or thermogenic (contaminant hydrocarbons). Map plots of C₁ to C₇ total interstitial hydrocarbons, C₂ to C₇ interstitial hydrocarbons, and C₁/C _n rations are used to further delineate and document the extent and migration of contamination.Three case studies of the technique are presented: each involves leakage of hydrocarbons from underground storage tanks. Soil gas analysis clearly defines the spread of contamination and can serve as the basis for the correct placement of monitoring wells. The method proved to be accurate, rapid, and cost-effective; it therefore has potential for widespread application to the identification of soil and groundwater contaminated by hydrocarbons.     

Effects of Ageing and Microbial Component on Chemical Availability of 137Cs in a Long-term Experimental Site

A loamy soil contaminated with ¹³⁷CsCl 40 years ago was investigated by a sequential extraction technique to determine the effect of ageing on chemical availability of ¹³⁷Cs. The soil samples were sequentially extracted with H₂O, NH₄Ac, NH₂OH·HCl, H₂O₂, and HNO₃. Extractability of ¹³⁷Cs decreased in the order: HNO₃ > Residual > H₂O₂ > NH₄Ac > NH₂OH·HCl > H₂O. Only 0.94% in labile fractions (H₂O and NH₄Ac), while more than 96% was found in the strongly bound fraction (HNO₃ and residual). However, the activity percentage in labile fractions was increased to 1.34% after autoclaving treatment, while those in the other fractions did not significantly differ. This indicates that the microbial activity played a role in the ¹³⁷Cs retention. In the subsequent pot experiments with ryegrass and leek, specific activities in both plants were significantly higher in autoclaved soil than in non-autoclaved soil, and uptake of ¹³⁷Cs in the five cuts by ryegrass was 25% of the labile ¹³⁷Cs in the soil. In addition, a positive correlation was found between the amount of ¹³⁷Cs in labile fractions and that by plant uptake.     

Aliphatic and polycyclic aromatic hydrocarbons in sediments of the Slovenian coastal area (Gulf of Trieste, northern Adriatic)

The distribution and sources of aliphatic and polycyclic aromatic hydrocarbons (PAH) were determined in sediments at seven sites around the Slovenian coastal area. The potential toxicological significance was also assessed using biological thresholds. The results of the analyses showed higher concentrations of hydrocarbons in the Port of Koper and in the Marina of Portoroz. The influence of pollution was also evident in rather higher concentrations of hydrocarbons in the surrounding area in the Bays of Koper and Piran. Concentrations of hydrocarbons decrease toward the central part of the Gulf of Trieste. The major component of the aliphatic fraction was the unresolved complex mixture. Concentrations of the total resolved aliphatic hydrocarbons were in a range from 689 to 3,164?ng?g^?1. Concentrations of the total PAHs were between 330 and 1,173?ng?g^?1. Polycyclic aromatic hydrocarbons are primarily of pyrolytic origin with some smaller contributions of the petrogenic, while the aliphatic are mostly of petrogenic origin with significant amounts of biogenic derived compounds of terrestrial and marine origin. Strong evidence of the diagenetic origin of perylene in the investigated area was also found. Quite a good linear relationship between PAH concentration and TOC and between aliphatic hydrocarbon concentrations and TOC was observed. The principal component analysis showed differences between the nearshore and offshore sites. In general, the investigated area is moderately contaminated by hydrocarbons. Concentrations of PAHs, hydrocarbons of high concern, are below the levels (effects range low and the effects range median) associated with adverse biological effects.     

Structural characterisation of macromolecular organic material in air particulate matter using Py-GC-MS and solid state 13C-NMR

Organic air particulate matter was analysed by applying the techniques of Py-GC-MS (pyrolysis-gas chromatography-mass spectrometry) and solid state 13C-NMR (nuclear magnetic resonance). Particles dislodged from air particulate filters and humic acid extracted from these filters were studied for structural components. The structural components of the air particles and extracted humic acid consisted of compounds originating from biomacromolecules, namely, lignin, carbohydrates, protein and lipids. The main components identified for each class included: (1) methoxyphenols originating from lignin; (2) furans, aldehydes and ketones from carbohydrates; (3) pyrrole, indoles from protein; and (4) many hydrocarbons from lipid structures. Single ion monitoring (SIM) and tetramethyl ammonium hydroxide (TMAH) methylation were utilised for detection of aliphatic hydrocarbons and acidic components, respectively. Hydrocarbons ranging from C9 to C28 were detected by SIM analysis, while aliphatic acids ranged from C9 to C18. The majority of components analysed directly in the air particles were similar to those from the humic acid extracts. Many of the structural components of air particles were typical of humic substances of soil and aqueous systems and these were attributed to both biogenic and anthropogenic sources.     

Identification of polycyclic aromatic hydrocarbons in unleaded petrol and diesel exhaust emission

Inhalation of emissions from petrol and diesel exhaust particulates is associated with potentially severe biological effects. In the present study, polycyclic aromatic hydrocarbons (PAHs) were identified from smokes released by the automobile exhaust from petrol and diesel. Intensive sampling of unleaded petrol and diesel exhaust were done by using 800-cm³ motor car and 3,455-cm³ vehicle, respectively. The particulate phase of exhaust was collected on Whatman filter paper. Particulate matters were extracted from filter paper by using Soxhlet. PAHs were identified from particulate matter by reverse phase high performance liquid chromatography using C₁₈ column. A total of 14 PAHs were identified in petrol and 13 in case of diesel sample after comparing to standard samples for PAH estimation. These inhalable PAHs released from diesel and petrol exhaust are known to possess mutagenic and carcinogenic activity, which may present a potential risk for the health of inhabitants.     

Redistribution of zinc, cadmium, and lead among soil fractions in a sandy calcareous soil due to application of poultry litter

This study was conducted to evaluate, using soil columns, the mobilization and redistribution of heavy metals (Zn, Cd, and Pb) among different soil fractions by soluble organic ligands within poultry litter. Uncontaminated soil was amended with Zn, Cd, and Pb to achieve concentration levels of 400, 8, and 200 mg kg⁻¹ soil, respectively. Columns repacked with this amended soil were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl₂, or poultry litter extract (PLE) solutions. After leaching, the soil samples in the columns were sequentially extracted for exchangeable (EXC), carbonate (CARB) organic matter (OM), Mn oxide (MNO), Fe oxide (FEO), and residual (RES) fractions. Considerable mobilization of Zn, Cd, and Pb occurred in soil during EDTA leaching. Leaching with PLE and CaCl₂ solutions significantly decreased Zn and Cd concentrations in the EXC, CARB, and OM fractions. These solutions significantly decreased Pb concentration in the EXC fraction, while PLE solubilized more Pb from EXC fraction than CaCl₂. Thus, the applied poultry litter may change Zn, Cd, and Pb fractions in metal-amended soil and possibly enhance metal mobility.     

Rate-Limited Desorption of Volatile Organic Compounds from Soils and Implications for the Remediation of a Louisiana Superfund Site

The rates of desorption of trichloroethylene (TCE) and 1,3-dichlorobenzene (DCB) from a silty soil at a Superfund site and a silty-clayey soil from an uncontaminated bottomland hardwoodswamp in Baton Rouge, Louisiana were studied in laboratory batchsystems. The effect of the age of soil contamination was studiedusing a laboratory-spiked soil incubated for 3 days, 3 months and5 months. An empirical non-linear model was used to describe thebi-phasic nature of desorption with one fraction (labile) beingreleased in relatively short periods of time (typically 24–100 hr) and a second fraction (non-labile or irreversible) beingresistant to desorption. The non-linear model parameters, viz.,the fraction of the chemical released rapidly (F), and the firstorder desorption rate coefficients, k ₁ and k ₂respectively for the labile and slowly released fractions weredetermined by fitting the experimental data to the model. Thedata fit the model well as indicated by the high r ² values.The estimate of k ₁ was good. However, the values of k ₂are known with less precision due to the limited duration of theexperiment and number of samples taken at long times. In addition, desorption kinetics of 3 and 5-month old contaminatedsoils showed that progressively less amount of contaminant was available for facile desorption (lower F) compared to freshly contaminated soil. The labile fraction had desorption rate constants of the order of 10^-1 h^-1, whereas the slowlyreleased fraction had rate constants of the order of 10^-4 h^-1 in accord with literature reported values for a varietyof other compounds and soils. Possible mechanisms describing these rates and implications for the site clean up are discussed.     

Role of carbonyls and aromatics in the formation of tropospheric ozone in Rio de Janeiro,Brazil

The ozone in Rio de Janeiro has been in violation of national air quality standards. Among all of the monitoring stations, the Bangu neighbourhood has the most violations of the national standard of 160 μg m^?3 for the years 2012 and 2013. This study evaluated the reactivity of the carbonyls and aromatics in the tropospheric ozone formation processes. The samples were collected between July and October of 2013. Carbonyls were sampled using SiO₂ cartridges coated with C₁₈ and impregnated with 2,4-dinitrophenylhydrazine and were analysed by HPLC. Activated carbon cartridges and GC/MS were used to measure the concentration of monoaromatic hydrocarbons. An air quality monitoring station provided the concentrations of the criteria pollutants and the meteorological parameters. Cluster analysis and a Pearson correlation matrix were used to determine the formation of groups and the correlation of the variables. The evaluation of the volatile organic compounds (VOC) reaction with OH radicals and the MIR scale was used to extrapolate the reactivity of VOCs to the ozone formation. The average concentrations obtained were 19.7 and 51.9 μg m^?3 for formaldehyde and acetaldehyde, respectively. The mean concentrations obtained for aromatics were 1.5, 6.7, 1.5, 2.6 and 1.6 μg m^?3 for benzene, toluene, ethyl benzene, m+p-xylene and o-xylene, respectively. The cluster analysis indicated the presence of three similar groups, with one formed by gaseous criteria pollutants, another formed by the meteorological parameters, ozone and fine particles, and the last group formed by the aromatics. For the two reactivity scales evaluated, acetaldehyde and toluene were the main ozone precursors.     

The Distribution and Sources of Polycyclic Aromatic Hydrocarbons in Surface Sediments Along the Egyptian Mediterranean Coast

Coastal marine sediment samples were collected from 31 sampling stations along the Egyptian Mediterranean Sea coast. All sediment samples were analyzed to determine aliphatic and polycyclic aromatic hydrocarbons (PAHs) as well as total organic carbon (TOC) contents and grain size analysis. Total concentrations of 16 EPA-PAHs in the sediments were varied from 88 to 6338 ng g⁻¹ with an average value of 154 ng g⁻¹ (dry weight). However, the concentrations of total aliphatic were varied from 1.3 to 69.9 ng g⁻¹ with an average value of 15.6 ng g⁻¹ (dry weight). The highest contents of PAHs were found in the Eastern harbor (6338 ng g⁻¹), Manzala (5206 ng g⁻¹) and El-Jamil East (4895 ng g⁻¹) locations. Good correlations observed between a certain numbers of PAH concentrations allowed to identify its origin. The average total organic carbon (TOC) percent was varied from 0.91 to 4.54%. Higher concentration of total pyrolytic hydrocarbons (∑COMB) than total fossil hydrocarbons (∑PHE) declared that atmospheric fall-out is the significant source of PAHs to marine sediments of the Egyptian Mediterranean coast. The selected marked compounds, a principal component analysis (PCA) and special PAHs compound ratios (phenanthrene/anthracene vs fluoranthene/pyrene; ∑COMB/∑EPA-PAHs) suggest the pyrogenic origins, especially traffic exhausts, are the dominant sources of PAHs in most locations. Interferences of rather petrogenic and pyrolytic PAH contaminations were noticed in the harbors due to petroleum products deliveries and fuel combustion emissions from the ships staying alongside the quays.     

Concentrations, sources, and exposure profiles of polycyclic aromatic hydrocarbons (PAHs) in particulate matter (PM10) in the north central part of India

Airborne particulates (PM₁₀) from four different areas within Agra city (a semi-arid region) were collected using respirable dust samplers during the winter season (Nov. 2005–Feb 2006) and were then extracted with methylene chloride using an automated Soxhlet Extraction System (Soxtherm^®). The extracts were analyzed for 17 target polycyclic aromatic hydrocarbons (PAHs) and the heterocycle carbazole. The average concentration of total PAH (TPAH) ranged from 8.04 to 97.93 ng m^???3. The industrial site had the highest TPAH concentration followed by the residential, roadside, and agricultural sites. Indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, and benzo(b)fluoranthene were the predominant compounds found in the samples collected from all of the sites. The average B(a)P-equivalent exposure, calculated by using toxic equivalent factors derived from literature and the USEPA, was approximately 7.6 ng m^???3. Source identification using factor analysis identified prominent three, four, four, and four probable factors at industrial, residential, roadside, and agricultural sites, respectively.     

飞行时间二次离子质谱法在一次污染过程中PM2.5表面组分分析中的应用

团簇离子源的发明和使用,使飞行时间二次离子质谱（TOF-SIMS）法成为材料表面化学分析越来越重要的手段,TOF-SIMS法的主要测试功能包括表层质谱、化学成像及深度剖析3种。采用TOF-SIMS法对一次污染过程中的大气细颗粒物（PM_2.5）的表层进行检测,得到了PM_2.5表面成分的质谱及成像信息。结果表明：PM_2.5表层存在多种金属离子,通过扫描电子显微镜能谱仪的形貌与飞行时间二次离子质谱仪的成像亮度分析可知,K⁺、Na⁺、Mg²⁺响应强度相对较强,含量较高;通过原子吸收光谱仪进行金属离子定量可知,2018年11月4日和12月24日的K⁺、Na⁺、Mg²⁺的平均质量分别为1.809 5、0.443 8、1.526 2 mg;从形态分布上看,PM_2.5表面烟尘集合体含量较多,其次为燃煤飞灰、矿物颗粒和超细未知颗粒;PM_2.5表层的有机物离子C_xH_y片段也较多,经过m/z的测试数据进一步确定,表明颗粒物表层含有大量的脂肪烃和芳香烃;除此之外,还存在含N、O、S等的有机物和无机物。     

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.     

Some soil properties on coal mine spoils reclaimed with black locust (Robinia pceudoacacia L.) and umbrella pine (Pinus pinea L.) in Agacli-Istanbul

This study performed on randomly selected seven sample plots in leguminous black locust (Robinia pceudoacacia L.) plantations and five sample plots in umbrella pine (Pinus pinea L.) plantations on coal mine soil/spoils. Soil samples were taken from eight different soil depths (0–1, 1–3, 3–5, 5–10, 10–20, 20–30, 30–40, and 40–50 cm) into the soil profile. On soil samples, bulk density, fine soil fraction (Ø < 2 mm), sand, silt and clay rates, soil acidity (pH), organic carbon (C_org), and total nitrogen (N_t) contents were investigated. Also, some forest floor properties (unit mass, organic matter, and total nitrogen) were determined, and results were compared statistically between umbrella pine and black locust. As a result, 17 years after plantations, total forest floor accumulation determined as 6,107 kg ha^???1 under black locust compared to 13,700 kg ha^???1 under umbrella pine. The more rapid transformation of leguminous black locust forest floor creates organic carbon that migrates further into the mineral profile, and rapid accumulation of C and N in the soil profile was registered. Slower transformation processes of forest floor under umbrella pine result in lower soil N ratio and greater quantity of forest floor. Higher soil pH under leguminous black locust was determined significantly than umbrella pine. In conclusion, the composition of symbiotic nitrogen fixation of black locust appears to be a possible factor favoring carbon and nitrogen accumulation and, consequently, soil development. Clearly, both tree species have favorable impacts on initial soil formation. The umbrella pine generates the more forest floor layer; in contrast, black locust forest floor incorporates into the soil more rapidly and significantly increases soil nitrogen in upper soil layers.     

Composition and sources of aliphatic lipids and sterols in sediments of a tropical island, southern South China Sea: preliminary assessment

Near-shore surface sediment was collected from five stations off Redang Island located on the eastern coast of Peninsular Malaysia. Freeze-dried sediments were Soxhlet extracted and then fractionated using column chromatography into aliphatic and polar fractions. Determination of these fractions was carried out using gas chromatography mass spectrometry. The concentration of total resolved aliphatic hydrocarbons in sediments ranged from 157 to 308 ng/g. The distribution of aliphatic fraction showed the presence of n-alkanes ranging from nC15 to nC33 with a minor odd-to-even predominance exhibiting carbon maximum, depending on station, at nC17, nC26, nC29 or nC31. Calculation of Carbon Preference Index (CPI) for CPI_15–33 gave values ranging from 1.09 to 1.46. n-Alkanol in all sediment exhibits even-to-odd carbon predominance ranging from nC16 to nC28 and maximising at nC22. n-Fatty acids distribution ranged from nC14 to nC24 with a dominant maximum at nC16 and exhibiting high values of short chain fatty acids (≤nC20) to long chain fatty acids (>nC20) ratios. Unsaturated fatty acids, particularly nC16:1 and nC18:1 is also ubiquitous in all samples. Cholesterol is the most abundant compound amongst the sterol group ranging from 42.8 to 62.6 % of the total sterols. β-Sitosterol, brassicasterol and stigmasterol, are also present but of relatively lower amount. These observations suggest that the aliphatic lipids and sterols in the study area originate, mainly, from biogenic sources of marine microbial with minor contribution from epiticular waxes of terrestrial plants.     

Emissions of NO and N2O from soils

Nitric oxide (NO) and nitrous oxide (N₂O) fluxes were measured from agricultural, forest and moorland environments, using chamber techniques. Maximum emissions of NO and N₂O were measured from the agricultural soils shortly after fertiliser application (7 ng NO-N m^–2 s^–1 and 91 ng N₂O-N m^–2 s^–1). For the non-agricultural soils the NO flux ranged from –0.3 to 0.5 ng NO-N m^–2 s^–1 and the N₂O flux ranged from 1 to 2.7 ng N₂O-N m^–2 s^–1. Emissions, however, were increased 2 to 7 fold when N deposition (uplands) and N fixation (alder plantations) contributed to the pool of soil available N. The best predictors of the NO emission were soil NO ₃ ^– and soil temperature, accounting for 60% of the variability observed. The prediction of N₂O was less successful. Only 30% of the variability could be explained by the soil NO ₃ ^– and the soil moisture content, soil temperature did not have a significant effect on the N₂O emission.     

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.     

Analysis of volatile organic compounds (VOCs) in sediments using in situ SPME sampling

A new method of determining the composition of sediment/soil gases and their volatile organic compound (VOC) content is described. VOCs were collected in situ from intertidal sediments in the Menai Strait and surrounding areas. The sampling was performed using a portable sampler comprising a funnel coupled to a SPME fibre. Gases were extracted from the sediments using a small vacuum pump pulling 100 mL min(-1) at atmospheric pressure. Sixty one different compounds were detected in the samples, and their fluxes and concentrations were determined. The compounds were classified into groups: halogenated, sulfur containing compounds, aldehydes, BTEXs (benzene, toluene, ethyl benzene and xylene) and aliphatic hydrocarbons. Results of principal component analysis (PCA) showed that the chemical composition of extracted gas was influenced primarily by sediment type. Muddy anoxic sediments were dominated by halogenated and sulfur containing compounds and sandy sediments had more aldehydes and BTEXs.