Fringe-controlled natural attenuation of phenoxy acids in a landfill plume: integration of field-scale processes by reactive transport modeling

Data obtained from a field study of an aquifer contaminated by landfill leachate and related laboratory experiments suggest that natural attenuation of phenoxy acid herbicides such as mecoprop (MCPP) occurs in the transition zone between the anaerobic plume core and the overlying aerobic water body. The location of this transition zone is assumed to be primarily controlled by vertical transverse dispersion processes occurring downstream of the pollution source. A reactive transport modeling study was carried out to evaluate this conceptual model. The transport was simulated for a two-dimensional vertical cross section to quantify the combined physical, geochemical, and microbial processes that affect the fate of the phenoxy acid herbicides. The simulations, showing removal of phenoxy acids, an increase of phenoxy acid degraders in the fringe zone, and a dependency of the results on vertical transverse dispersivity, are compatible with the hypothesis of fringe-controlled aerobic biodegradation of the phenoxy acids.     

Effect of exposure history on microbial herbicide degradation in an aerobic aquifer affected by a point source

The effects of in situ exposure to low concentrations (micrograms per liter) of herbicides on aerobic degradation of herbicides in aquifers were studied by laboratory batch experiments. Aquifer material and groundwater were collected from a point source with known exposure histories to the herbicides mecoprop (MCPP), dichlorprop, BAM, bentazone, isoproturon, and DNOC. Degradation of the phenoxy acids, mecoprop and dichlorprop, was observed in five of six sampling points from within the plume. Mecoprop was mineralized, and up to 70% was recovered as 14CO2. DNOC was degraded in only two of six sampling points from within the plume, and neither BAM, bentazone, nor isoproturon was degraded in any sampling point. A linear correlation (R2 > or = 0.83) between pre-exposure and amount of herbicide degraded within 50 days was observed for the phenoxy acids, mecoprop and dichlorprop. An improved model fit was obtained from using Monod degradation kinetics compared to zero- and first-order degradation kinetics. An exponential correlation (R2 > or = 0.85) was also found between numbers of specific phenoxy acid degrading bacteria and pre-exposure. Combination of these results strongly indicates that the low concentration exposure to phenoxy acids in the aquifer resulted in the presence of acclimated microbial communities, illustrated bythe elevated numbers of specific degraders as well as the enhanced degradation capability. The findings support application of natural attenuation to remediate aerobic aquifers contaminated by phenoxy acids from point sources.     

Can degradation products be used as documentation for natural attenuation of phenoxy acids in groundwater?

In situ indicators of degradation are important tools in the demonstration of natural attenuation. A literature survey on the production history of phenoxy acids and degradation pathways has shown that metabolites of phenoxy acid herbicides also are impurities in the herbicide products, making the bare presence of these compounds useless as in situ indicators. These impurities can make up more than 30% of the herbicides. Degradation of phenoxy acids was demonstrated in microcosm experiments using groundwater and sediment contaminated with MCPP, dichlorprop, and related compounds such as other phenoxypropionic acids and chlorophenols. Field observations at two phenoxy acid-contaminated sites showed the occurrence of several impurities including metabolites in the groundwater. Neither the microcosm experiments nor the field observations verified that metabolites were actually produced or accumulated in situ. However, it was demonstrated that the impurity/parent herbicide ratios can be useful in situ indicators of degradation.     

Natural occurrence of hexavalent chromium in the Aromas Red Sands Aquifer, California

To address increasing concerns of chromium contamination in the drinking water of Santa Cruz County, we designed a study to investigate the source(s) and spatial gradients of the chromium concentration and speciation in local aquifers. This study was catalyzed by a report (January 2001) bythe Soquel Creek Water District of elevated hexavalent chromium concentrations ranging from 6 to 36 microg L(-1), approaching the state's maximum concentration limit of 50 microg L(-1), in the Aromas Red Sands aquifer. To test the accuracy of those preliminary measurements, we collected groundwater using trace metal clean techniques from 11 sites in Santa Cruz County, including 10 from the aquifer with reportedly elevated chromium concentrations and 1 from an adjacent aquifer, the Purisima, and analyzed them fortotal chromium using inductively couple plasma mass spectrometry. Nine of the reportedly 10 contaminated sites had total chromium concentrations ranging from 5 to 39 microg L(-1), while one from the control site was below the limit of detection (0.01 microg L(-1)). We also measured the speciation of chromium at all sites using a solid supported membrane extraction coupled with graphite furnace atomic absorption spectrometry and determined that on average 84% of total chromium was Cr(VI). In addition to the groundwater analyses, a series of extractions were performed on sediment samples from both the Aromas Red Sands and Purisima aquifers. These tests were used to empirically characterize sediment trace metal (Cr, Fe, Mn) distributions in five phases providing information about the origin, availability, reactivity, and mobilization of these trace metals. Results from groundwater and sediment samples indicate that the chromium is naturally occurring in the Aromas Red Sands aquifer, possibly by Cr(III) mineral deposits being oxidized to Cr(VI) by manganese oxides in the aquifer.     

Leaching and primary biodegradation of sulfonated naphthalenes and their formaldehyde condensates from concrete superplasticizers in groundwater affected by tunnel construction

Sulfonated naphthalenes and their formaldehyde condensates (SNFC) are used as concrete superplasticizers fortunnel construction through aquifers.This paperdiscusses their primary biodegradation in groundwater affected by construction activities. The analyses of groundwater samples collected 5 m away from a construction site clearly indicated that components of the applied SNFC product leached into the groundwater. A maximum total concentration of these compounds of 233 microg/L was found, and it was shown that only the monomeric sulfonated naphthalenes andthe condensates uptothetetramerleached in substantial amounts. The decrease in concentration of several monomeric components could not be explained by mere dispersion but rather indicates a biological transformation in the aquifer. This was confirmed at a second field site and by laboratory degradation experiments with piezometer material as inoculum. Lag phases for the individually degradable sulfonated naphthalenes ranged from 0 to 96 d. Naphthalene-1,5-disulfonate and the oligomeric components were neither degraded in the aquifer nor in the laboratory experiments within an observation time of up to 195 d. This clearly indicates their persistence in subsurface waters.     

Degradation of carbendazim and 2,4-dichlorophenoxyacetic acid by immobilized consortium on loofa sponge

A fungicide, carbendazim (methyl-2-benzimidazole carbamate; MBC), and a herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), could be simultaneously degraded by a microbial consortium obtained from several soil samples in Japanese paddy fields with enrichment continuous culture. The degradation ability of the consortium was increased by immobilization on loofa (Luffa cylindrica) sponge in comparison with that of free-living consortium. MBC and 2,4-D were completely degraded within 5.5 d and 1.5 d, respectively. The toxicity of these pesticides in culture medium to Daphnia magna was reduced by treatment with the consortium corresponding to their degradation. The degradation ability of the immobilized consortium at pHs in the range from 6 to 9, at temperatures from 15 degrees C to 37 degrees C, and at low NH(4)(+)-N concentrations (1-10 mg/l) was not very different from that under the basal condition (pH 7, 30 degrees C, 424 mg/l NH(4)(+)-N and 472 mg/l PO(4)(3)(-)-P). At low pHs 4 and 5, the ability was significantly lower than that of the basal condition. Moreover, incubation at low PO(4)(3)(-)-P concentrations (1-10 mg/l) caused a decrease in pH at which the degradation ability also became lower. However, the ability in this culture completely recovered when pH was adjusted to 7 or the phosphate concentration was increased to the basal level. Analysis by denaturing gradient gel electrophoresis (DGGE) showed the whole population of the consortium became faint at low pH or low phosphate concentrations but became distinct again as much as those under the basal conditions, indicating that the decrease in the degradation ability caused by low pH was due to that whole population of the consortium underwent serious damage but could survive and recover. These results suggest the immobilized consortium on loofa sponge is a promising material for bioremediation of polluted water with these pesticides in paddy fields.     

Formation and fate of bound residues from microbial biomass during 2,4-D degradation in soil

During organic contaminant degradation in soil, bound or nonextractable residues (NER) are formed. Part of these residues may be biogenic, because degrading microorganisms assimilate carbon derived from the pollutant and mineralized CO(2) to form cellular components for example, [fatty acids (FA) and amino acids (AA)], which are subsequently stabilized within soil organic matter (SOM). We investigated the formation and fate of FA and AA from biodegradation of (13)C(6)-2,4-D in soil and the incorporation of the (13)C-label into living biomass via (13)CO(2) fixation. After 64 days of incubation, (13)C-AA in SOM indicated that 44% of the initially applied (13)C(6)-2,4-D equivalents had been converted to microbial biomass and finally to biogenic residues. The intermediate maximum of (13)C-FA in SOM indicated a 20% conversion of (13)C(6)-2,4-D to biomass, but (13)C-FA decreased to 50% of that value whereas (13)C-AA in the SOM remained stable. We provide the first evidence that nearly all bound residues from 2,4-D are biogenic, containing natural microbial residues stabilized in SOM. Because of biogenic residue formation, the potential risk of bound residues from readily metabolized xenobiotics in soils is highly overestimated. Hence, the formation of biogenic residues must be considered in general when performing mass balances of pollutant biodegradation in soils.     

影响大杯伞菌丝体及胞外多糖的几种因子的研究

本文主要研究了不同浓度的NAA、2,4-D、IBA、L-GLU、油酸,CMC六种因子对大杯伞深层培养菌丝体得率和胞外多糖的影响,并筛选出最适浓度。实验结果表明,当NAA为0.4mg/L、2,4-D为0.3mg/L、L-Glu为0.5～1.0mg/L、IBA为1.0mg/L,油酸为0.2～0.3mg/L、CMC为0.3mg/L时为其菌丝体生长的适宜浓度;胞外多糖产生的最适浓度为:NAA0.1mg/L、2,4-D0.3mg/L、L-Glu1.0mg/L、IBA为1.5mg/L,油酸0.4mg/L、CMC0.5mg/L。     

Combined application of stable carbon isotope analysis and specific metabolites determination for assessing in situ degradation of aromatic hydrocarbons in a tar oil-contaminated aquifer

To evaluate the intrinsic bioremediation potential in an anoxic tar oil-contaminated aquifer at a former gasworks site, groundwater samples were qualitatively and quantitatively analyzed by compound-specific isotope analysis (CSIA) and signature metabolites analysis (SMA). 13C/12C fractionation data revealed conclusive evidence for in situ biodegradation of benzene, toluene, o-xylene, m/p-xylene, naphthalene, and 1-methylnaphthalene. In laboratory growth studies, 13C/12C isotope enrichment factors for anaerobic degradation of naphthalene (epsilon = -1.1 +/- 0.4) and 2-methylnaphthalene (epsilon = -0.9 +/- 0.1) were determined with the sulfate-reducing enrichment culture N47, which was isolated from the investigated test site. On the basis of these and other laboratory-derived enrichment factors from the literature, in situ biodegradation could be quantified for toluene, o-xylene, m/p-xylene, and naphthalene. Stable carbon isotope fractionation in the field was also observed for ethylbenzene, 2-methylnaphthalene, and benzothiophene but without providing conclusive results. Further evidence for the in situ turnover of individual BTEX compounds was provided by the presence of acetophenone, o-toluic acid, and p-toluic acid, three intermediates in the anaerobic degradation of ethylbenzene, o-xylene, and p-xylene, respectively. A number of groundwater samples also contained naphthyl-2-methylsuccinic acid, a metabolite that is highly specific for the anaerobic degradation of 2-methylnaphthalene. Additional metabolites that provided evidence on the anaerobic in situ degradation of naphthalenes were 1-naphthoic acid, 2-naphthoic acid, 1,2,3,4-tetrahydronaphthoic acid, and 5,6,7,8-tetrahydronaphthoic acid. 2-Carboxybenzothiophene, 5-carboxybenzothiophene, a putative further carboxybenzothiophene isomer, and the reduced derivative dihydrocarboxybenzothiophene indicated the anaerobic conversion of the heterocyclic aromatic hydrocarbon benzothiophene. The combined application of CSIA and SMA, as two reliable and independent tools to collect direct evidence on intrinsic bioremediation, leads to a substantially improved evaluation of natural attenuation in situ.     

In situ assessment of biodegradation potential using biotraps amended with 13C-labeled benzene or toluene

Stable isotope fractionation analysis of an aquifer heavily contaminated with benzene (up to 850 mg L(-1)) and toluene (up to 50 mg L(-1)) at a former hydrogenation plant in Zeitz (Saxonia, Germany) has suggested that significant biodegradation of toluene was occurring. However, clear evidence of benzene biodegradation has been lacking at this site. Determining the fate of benzene is often a determining factor in regulatory approval of a risk-based management strategy. The objective of the work described here was the demonstration of a new tool that can be used to provide proof of biodegradation of benzene or other organics by indigenous microorganisms under actual aquifer conditions. Unique in situ biotraps containing Bio-Sep beads, amended with 13C-labeled or 12C nonlabeled benzene and toluene, were deployed at the Zeitz site for 32 days in an existing groundwater monitoring well and used to collect and enrich microbial biofilms. Lipid biomarkers or remaining substrate was extracted from the beads and analyzed by mass spectrometry and molecular methods. Isotopic analysis of the remaining amounts of 13C-labeled contaminants (about 15-18% of the initial loading) showed no alteration of the 12C/13C ratio during incubation. Therefore, no measurable exchange of labeled compounds in the beads by the nonlabeled compounds in the aquifer materials occurred. Isotopic ratio analysis of microbial lipid fatty acids (as methyl ester derivatives) from labeled benzene- and toluene-amended biotraps showed 13C enrichment in several fatty acids of up to delta (13C) 13400%o, clearly verifying benzene and toluene biodegradation and the transformation of the labeled carbon into biomass by indigenous organisms under aquifer conditions. Fatty acid profiles of total lipid fatty acids and the phospholipid fatty acid fraction and their isotopic composition showed significant differences between benzene- and toluene-amended biotraps, suggesting that different microbial communities were involved in the biodegradation of the two compounds.     

Nondestructive,minimal-disturbance,direct-burial solid-phase microextraction fiber technique for measuring TNT in sediment

We explored a novel technique to deploy solid-phase microextraction (SPME) fibers to nondestructively measure the explosive compound 2,4,6-trinitrotoluene (TNT) and its nitroaromatic (NA) degradation products in laboratory sediment toxicity tests and field sediments in situ. SPME fibers within steel mesh envelopes were exposed statically via direct burial within sediment. Six fiber types (polymer coatings) were tested. Polyacrylate (PA) SPME fiber was sufficiently durable for this application, yielded the lowest detection limits, and exhibited a linear uptake relationship across toxicologically relevant sediment NA concentrations (100-2000 nmol/g dw (20-500 microg/g dw)). Temperature greatly influenced SPME absorption kinetics. Via evaluation of absorption at different temperatures, recommended sampling times needed to achieve steady-state equilibrium were 48 h for room temperatures (23-25 degrees C) and up to 7 d for cold (5 degrees C) temperatures. Although a comparison of TNT residues by SPMEs and TNT bioavailability and toxicity in sediments has not been completed, differences in SPME availability of TNT and its degradation products were found between two different TNT-spiked sediments. Our disposable SPME technique was slightly less expensive and as precise as the conventional extraction for total NAs and may prove to be a powerful exposure evaluation tool for assessing the ecological risk of these compounds.     

Hydrogen and carbon isotope fractionation during anaerobic biodegradation of aromatic hydrocarbons--a field study

The aquifer of a former manufactured gas plant site, highly contaminated by dissolved monocyclic, heterocyclic, and polycyclic aromatic hydrocarbons, was studied to evaluate the applicability of carbon and hydrogen isotope fractionation to prove ongoing biodegradation of these compounds even in complex aquifer settings. The loss of toluene, o-xylene, p,m-xylene, and 2-methylnaphthalene was accompanied by a considerable carbon isotope fractionation. Additionally, a strong 2H enrichment in residual o-xylene was detected. All isotope fractionations observed could be related to established biochemical degradation mechanisms, each involving a C-H bond cleavage in the rate-determining step. In contrast, other compounds such as 1-methylnaphthalene, methylbenzofuran, and acenaphthene exhibited a uniform stable carbon isotope composition. However, a decrease in concentration for these compounds was observed in the flowpath of the aquifer. High threshold concentrations of acenaphthene downgradient indicate that this contaminant is, if at all, only marginally biodegraded. Detailed analyses of xylenes provided support that compound specific isotope analyses and subsequent application of the Rayleigh model may provide a valuable basis to distinguish between different biodegradation mechanisms as well as dissolution processes in heterogeneous aquifers.     

Effect of planting covers on herbicide persistence in landscape soils

Recent monitoring shows that the majority of urban streams in the United States are contaminated by pesticide residues, and the contamination is mainly due to runoff from residential landscapes. In this study we evaluated the effect of landscape planting on persistence of the herbicides 2,4-D and dicamba in soil under laboratory conditions. The herbicides exhibited substantially different persistence in the same soil type that had been subjected to different planting practices for about 6 years. In the 0-10 cm surface layer, the half-life of 2,4-D was 30.7 d in soil under trees, which was about 20 times longer than in soil planted with turf grass (1.6 d). The difference in 2,4-D persistence was closely correlated to the number of 2,4-D-degrading bacteria that had evolved in the soils. The half-life of dicamba was much longer in soil under a tree canopy (149 d) than in mulched soil (7.9 d). The rate of dicamba degradation was proportional to soil organic matter content. This study indicates that planting practices can modify soil chemical properties and microbial activity and may further affect pesticide runoff potential by influencing pesticide degradation. Characterizing pesticide behavior as a function of planting covers may improve our understanding of pesticide runoff in urban environments and also help to identify strategies for minimizing pesticide contamination to urban streams.     

Metabolites indicate hot spots of biodegradation and biogeochemical gradients in a high-resolution monitoring well

Anaerobic degradation processes play an important role in contaminated aquifers. To indicate active biodegradation processes signature metabolites can be used. In this study field samples from a high-resolution multilevel well in a tar oil-contaminated, anoxic aquifer were analyzed for metabolites by liquid chromatography-tandem mass spectrometry and time-of-flight mass spectrometry. In addition to already known specific degradation products of toluene, xylenes, and naphthalenes, the seldom reported degradation products benzothiophenemethylsuccinic acid (BTMS), benzofuranmethylsuccinic acid (BFMS), methylnaphthyl-2-methylsuccinic acid (MNMS), and acenaphthene-5-carboxylic acid (AC) could be identified (BFMS, AC) and tentatively identified (BTMS, MNMS). The occurrence of BTMS and BFMS clearly show that the fumarate addition pathway, known for toluene and methylnaphthalene, is also important for the anaerobic degradation of heterocyclic contaminants in aquifers. The molar concentration ratios of metabolites and their related parent compounds differ over a wide range which shows that there is no simple and consistent quantitative relation. However, generally higher ratios were found for the more recalcitrant compounds, which are putatively cometabolically degraded (e.g., 2-carboxybenzothiophene and acenaphthene-5-carboxylic acid), indicating an accumulation of these metabolites. Vertical concentration profiles of benzylsuccinic acid (BS) and methyl-benzylsuccinic acid (MBS) showed distinct peaks at the fringes of the toluene and xylene plume indicating hot spots of biodegradation activity and supporting the plume fringe concept. However, there are some compounds which show a different vertical distribution with the most prominent concentrations where also the precursor compounds peaked.     

Occurrence of 2,4-dichlorophenol and of 2,4-dichloro-6-nitrophenol in the Rhone River Delta (Southern France)

The compounds 2,4-dichlorophenol (2,4-DCP) and 2,4-dichloro-6-nitrophenol (6-nitro-2,4-DCP) have been detected at microg L(-1) levels (10(-9)-10(-8) M) during the summer season 2005 in the water of the Rh?ne river delta. Compound 2,4-DCP would mainly derive from the transformation of the herbicide dichlorprop, heavily used in flooded rice farming (1400 kg in the delta region in 2005), in addition to being an impurity of the commercial herbicide. Field data show a fast concentration decrease of 2,4-DCP in the period June 21st to July 5th, accompanied by a corresponding increase of 6-nitro-2,4-DCP. This could imply a possible nitration process of 2,4-DCP into 6-nitro-2,4-DCP, with quite elevated yield (33%). Nitration of 2,4-DCP can be induced by photoproduced *NO2, the reaction kinetics (calculated in the presence of Fe(III) + nitrite under irradiation as model system) being d[6-nitro-2,4-DCP]/dt = 650 [2,4-DCP] [*NO2]. Interestingly, the yield of the process (38%) is similar to that suggested by field data. An indirect assessment of [*NO2] in surface water in different sites of the Rh?ne delta indicated that 2,4-DCP could be transformed into 6-nitro-2,4-DCP in a couple of weeks or less in the shallow water (10 cm depth) of the rice fields, a time scale that is compatible with field data. Photonitration of 2,4-DCP is thus a possible process to account for the occurrence of 6-nitro-2,4-DCP in the Rh?ne delta.     

Deposition and fate of arsenic in iron- and arsenic-enriched reservoir sediments

Deposition of arsenic to the sediments of Haiwee Reservoir (Olancha, CA) has dramatically increased since March 1996 as a result of an interim strategy for arsenic management in the Los Angeles Aqueduct (LAA) water supply. Ferric chloride and cationic polymer are introduced into the Aqueduct at the Cottonwood treatment plant, 27 km north of the Haiwee Reservoir. This treatment decreases the average arsenic concentration from 25 microg/L above Cottonwood to 8.3 microg/L below Haiwee. Iron- and arsenic-rich flocculated solids are removed by deposition to the reservoir sediments. Analysis of sediments shows a pronounced signature of this deposition with elevated sediment concentrations of iron, arsenic, and manganese relative to a control site. Sediment concentrations of these elements remain elevated throughout the core length sampled (ca. 4% iron and 600 and 200 microg/g of manganese and arsenic, respectively, on a dry weight basis). A pore water profile revealed a strong redox gradient in the sediment. Manganese in the pore waters increased below 5 cm; iron and arsenic increased below 10 cm and were strongly correlated, consistent with reductive dissolution of iron oxyhydroxides and concurrent release of associated arsenic to solution. X-ray absorption near-edge spectroscopy revealed inorganic As(V) present only in the uppermost sediment (0-2.5 cm) in addition to inorganic As(III). In the deeper sediments (to 44 cm), only oxygen-coordinated As(III) was detected. Analysis of the extended X-ray absorption fine structure spectrum indicates that the As(III) at depth remains associated with iron oxyhydroxide. We hypothesize that this phase persists in the recently deposited sediment despite reducing conditions due to slow dissolution kinetics.     

Fate of nonylphenol ethoxylates and their metabolites in two Dutch estuaries: evidence of biodegradation in the field

The environmental behavior of nonylphenol ethoxylates (A9PEO) and their metabolites was investigated in field studies in the two Dutch estuaries Western Scheldt and the Rhine estuary. Using liquid chromatography-electrospray mass spectrometry (LC-ES-MS) analysis after solid-phase extraction, A9PEO, nonylphenol (NP), and the carboxylated metabolites (A9PEC) were determined in surface water and sediments. Maximum dissolved concentrations of 2.3, 0.9, and 8.1 microg L(-1), respectively, were found. In sediments, maximum concentrations of 242 and 1080 ng g(-1) for A9PEO and NP were observed. In almost half of the sediment samples, concentrations of A9PEC in sediments were below the detection limit. Occasionally relatively high values were observed, with a maximum of 239 ng g(-1). Metabolites of the carboxy alkylphenoxy ethoxy acetic acids (CAPEC) type could not be detected in any of the sediment or water samples. In the Scheldt estuary, dissolved concentration profiles showed nonconservative behaviorfor all detected compound groups. While A9PEO and NP concentrations strongly decreased along the salinity gradient, this decrease was weaker for the A9PEC metabolites. The increasing concentration ratio of A9PEC/A9PEO clearly illustratesthe important role that aerobic biodegradation plays in the estuarine fate of these compounds. It is concluded that the oxidative hydrolytic degradation pathway is the main degradation route in this nonstratified estuary. At high salinities, where concentrations drop to background levels of around 50 ng L(-1), this ratio decreases to about unity. Simple model calculations show that this can be explained if continuous diffuse discharges (e.g. from the intensive shipping in the estuary) are assumed. For the stratified Rhine estuary the water concentration profiles are less pronounced, possibly due to more complicated and turbulent water flows and point sources from the Rotterdam harbors.     

Small-volume releases of gasoline in the vadose zone: impact of the additives MTBE and ethanol on groundwater quality

A controlled gasoline spill experiment was performed under outdoor conditions typical for winter in temperate regions to study the fate of methyl tert-butyl ether (MTBE), ethanol, benzene, and selected other petroleum hydrocarbons. Artificial gasoline containing MTBE and ethanol (5% w/w of each) was placed at a defined depth into a 2.3 m thick unsaturated zone of alluvial sand overlying a gravel aquifer in a lysimeter. During an initial period of 41 days without recharge, MTBE and hydrocarbon vapors migrated by vapor-phase diffusion to groundwater, while ethanol vapors were naturally attenuated. In a subsequent period of 30 days with 5-mm daily recharge, all soluble compounds including ethanol were transported to the groundwater. Ethanol disappeared concomitantly with benzene and all other petroleum hydrocarbons except isooctane from the aerobic groundwater due to biodegradation. MTBE persisted for longer than 6 months at concentrations larger than 125000 microg L(-1). No evidence for MTBE biodegradation was found, whereas > 99.6% of ethanol removal from the lysimeter was due to biodegradation. It is concluded that MTBE-free gasoline would be less harmful for groundwater resources and that ethanol is an acceptable substitute.     

Oxidation products of polyunsaturated fatty acids in infant formulas compared to human milk--a preliminary study

Information about lipid oxidation in fresh and stored human milk compared with infant formulas is scarce. We aimed to assess n-6 and n-3 PUFA oxidation in these milks by measuring the 4-hydroxynonenal (4-HNE) and 4-hydroxyhexenal (4-HHE) content. Human milk samples (n = 4), obtained from volunteer mothers, were analyzed fresh and after 1 wk at 4 degrees C or 24 h at 18 degrees C. Vitamin E and malondialdehyde (MDA) were measured by HPLC and fatty acid profile by GC. The 4-HHE and 4-HNE contents were measured by GC-MS. Infant formulas (n = 10) were tested; their fat droplet size was measured by laser light scattering and observed by confocal laser scanning microscopy. Human milk samples contained 31.0 +/- 6.3 g/L of lipids and 1.14 +/- 0.26 mg/L of vitamin E. Fat droplets were smaller in infant formulas than reported in human milk. The (4-HHE/n-3 PUFA) ratio was 0.19 +/- 0.01 microg/g in fresh human milk (unchanged after storage) versus 3.6 +/- 3.1 microg/g in dissolved powder formulas and 4.3 +/- 3.8 microg/g in liquid formula. (4-HNE/n-6 PUFA) was 0.004 +/- 0.000 microg/g in fresh milk (0.03 +/- 0.01 microg/g after storage) versus 1.1 +/- 1.0 microg/g in dissolved powder formulas and 0.2 +/- 0.3 microg/g in liquid formula. Infant formulas also contained more MDA than human milk. n-3 PUFA were more prone to oxidation than n-6 PUFA. Whether threshold levels of 4-HHE and 4-HNE would be of health concern should be elucidated.     

苯氧羧酸类除草剂残留检测技术的研究进展

以2,4-D为代表的苯氧羧酸类除草剂,低浓度为保花保果生长调节剂,调节细胞生长及愈伤的分化、提高保鲜时间,高浓度为除草剂,该类除草剂难降解,易污染地下水,广泛、大量的应用会使植物产生畸形,影响人体中枢神经系统,具有潜在的致癌性和致突变性。因此,快速、灵敏、准确地检测出苯氧羧酸类残留是保证农产品、环境安全的重要手段,本文概述了苯氧羧酸类除草剂的前处理方法及不同检测方法在检测农产品、环境水样等样品中苯氧羧酸类除草剂残留的研究进展。综合对比了色谱法、联合技术、免疫法、纳米材料及传感器等检测方法在苯氧羧酸类检测中应用的优缺点,提出了未来检测小分子物质的发展趋势。