Isotope tracing of submarine groundwater discharge offshore Ubatuba, Brazil: results of the IAEA–UNESCO SGD project

Results of groundwater and seawater analyses for radioactive (³H, ²²²Rn, ²²³Ra, ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra) and stable (D and ¹⁸O) isotopes are presented together with in situ spatial mapping and time series ²²²Rn measurements in seawater, direct seepage measurements using manual and automated seepage meters, pore water investigations using different tracers and piezometric techniques, and geoelectric surveys probing the coast. This study represents first time that such a new complex arsenal of radioactive and non-radioactive tracer techniques and geophysical methods have been used for simultaneous submarine groundwater discharge (SGD) investigations. Large fluctuations of SGD fluxes were observed at sites situated only a few meters apart (from 0 cm d⁻¹ to 360 cm d⁻¹; the unit represents cm³/cm²/day), as well as during a few hours (from 0 cm d⁻¹ to 110 cm d⁻¹), strongly depending on the tidal fluctuations. The average SGD flux estimated from continuous ²²²Rn measurements is 17 ± 10 cm d⁻¹. Integrated coastal SGD flux estimated for the Ubatuba coast using radium isotopes is about 7 × 10³ m³ d⁻¹ per km of the coast. The isotopic composition (δD and δ¹⁸O) of submarine waters was characterised by significant variability and heavy isotope enrichment, indicating that the contribution of groundwater in submarine waters varied from a small percentage to 20%. However, this contribution with increasing offshore distance became negligible. Automated seepage meters and time series measurements of ²²²Rn activity concentration showed a negative correlation between the SGD rates and tidal stage. This is likely caused by sea level changes as tidal effects induce variations of hydraulic gradients. The geoelectric probing and piezometric measurements contributed to better understanding of the spatial distribution of different water masses present along the coast. The radium isotope data showed scattered distributions with offshore distance, which imply that seawater in a complex coast with many small bays and islands was influenced by local currents and groundwater/seawater mixing. This has also been confirmed by a relatively short residence time of 1–2 weeks for water within 25 km offshore, as obtained by short-lived radium isotopes. The irregular distribution of SGD seen at Ubatuba is a characteristic of fractured rock aquifers, fed by coastal groundwater and recirculated seawater with small admixtures of groundwater, which is of potential environmental concern and has implications on the management of freshwater resources in the region.     

Spatial and temporal variations in groundwater nitrate at an intensive dairy farm in south-east Ireland: Insights from stable isotope data

Achievement of at least “good ecological status” in all waterbodies under the EU Water Framework Directive by 2015 will in some cases be a challenge. The twin challenge is to manage expectations of policy makers for such waterbodies as to a realistic length of time required for improvement in water quality. Hence, understanding the source, transformation processes and residence time of nitrate in a hydrological system is an essential part of meeting such challenges. On a dairy farm with 24 shallow groundwater wells, the dual isotopic composition of nitrate (δ¹⁵N and δ¹⁸O) was used to clarify nitrate sources, to assess spatial and temporal variability in nitrate concentrations and to determine if and where denitrification was occurring. Vertical travel time was estimated to correlate nitrate concentrations with management practices. Organically derived nitrogen was the predominant source contributing to groundwater nitrate concentrations. Denitrification was identified as prevalent within specific regions of the study site. The distinct low temporal variability in the isotopic data suggests constancy among nitrate sources and processes over time across the study site. Vertical travel times of up to 3 years were estimated on site indicating the influence of recent management practices on nitrate concentrations. Very slow horizontal migration of groundwater (decades) indicates a legacy of older management practices. Stable isotope techniques, together with an understanding of time lag, provide an extra mechanism to test the efficacy of monitoring and mitigation programmes.     

The stable isotope signature of methane emitted from plant material under UV irradiation

Recent experiments have shown that dry and fresh leaves, other plant matter, as well as several structural plant components, emit methane upon irradiation with UV light. Here we present the source isotope signatures of the methane emitted from a range of dry natural plant leaves and structural compounds. UV-induced methane from organic matter is strongly depleted in both ¹³C and D compared to the bulk biomass. The isotopic content of plant methoxyl groups, which have been identified as important precursors of aerobic methane formation in plants, falls roughly halfway between the bulk and CH₄ isotopic composition. C3 and C4/CAM plants show the well-established isotope difference in bulk ¹³C content. Our results show that they also emit CH₄ with different δ¹³C value. Furthermore, δ¹³C of methoxyl groups in the plant material, and ester methoxyl groups only, show a similar difference between C3 and C4/CAM plants. The correlation between the δ¹³C of emitted CH₄ and methoxyl groups implies that methoxyl groups are not the only source substrate of CH₄.Interestingly, δD values of the emitted CH₄ are also found to be different for C3 and C4 plants, although there is no significant difference in the bulk material. Bulk δD analyses may be compromised by a large reservoir of exchangeable hydrogen, but no significant δD difference is found either for the methoxyl groups, which do not contain exchangeable hydrogen. The δD difference in CH₄ between C3 and C4 plants indicates that at least two different reservoirs are involved in CH₄ emission. One of them is the OCH₃ group, the other one must be significantly depleted, and contribute more to the emissions of C3 plants compared to C4 plants. In qualitative agreement with this hypothesis, CH₄ emission rates are higher for C3 plants than for C4 plants.     

Isotopic modelling of the significance of bacterial sulphate reduction for phenol attenuation in a contaminated aquifer

A Triassic sandstone aquifer polluted with a mixture of phenolic hydrocarbons has been investigated by means of high-resolution groundwater sampling. Samples taken at depth intervals of 1 m have revealed the presence of a diving pollutant plume with a sharply defined upper margin. Concentrations of pollutant phenols exceed 4 g/l in the plume core, rendering it sterile but towards the diluted upper margin evidence for bacterial sulphate reduction (BSR) has been obtained. Groundwaters have been analysed for both delta34S-SO4 and delta18O-SO4. Two reservoirs have been identified with distinct sulphate oxygen isotope ratios. Groundwater sulphate (delta18O-SO4 = 3-5/1000) outside the plume shows a simple linear mixing trend with an isotopically uniform pollutant sulphate reservoir (delta18O-SO4 = 10-12/1000) across the plume margin. The sulphur isotope ratios do not always obey a simple mixing relation, however, at one multilevel borehole, enrichment in 34SO4 at the plume margin is inversely correlated with sulphate concentration. This and the presence of 34S-depleted dissolved sulphide indicate that enrichment in 34SO4 is the result of bacterial sulphate reduction. Delta34S analysis of trace hydrogen sulphide within the plume yielded an isotope enrichment factor (epsilon) of -9.4/1000 for present-day bacterial sulphate reduction. This value agrees with a long-term estimate (-9.9/1000) obtained from a Rayleigh model of the sulphate reduction process. The model was also used to obtain an estimate of the pre-reduction sulphate concentration profile with depth. The difference between this and the present-day profiles then gave a mass balance for sulphate consumption. The organic carbon mineralisation that would account for this sulphate loss is shown to represent only 0.1/1000 of the phenol concentration in this region of the plume. Hence, the contribution of bacterial sulphate reduction to biodegradation has thus far been small. The highest total phenolic concentration (TPC) at which there is sulphur isotope evidence of bacterial sulphate reduction is 2000 mg/l. We suggest that above this concentration, the bactericidal properties of phenol render sulphate-reducing bacteria inactive. Dissolved sulphate trapped in the concentrated plume core will only be utilised by sulphate reducers when toxic phenols in the plume are diluted by dispersion during migration.     

Microbial communities biostimulated by ethanol during uranium (VI) bioremediation in contaminated sediment as shown by stable isotope probing

Stable isotope probing (SIP) was used to identify microbes stimulated by ethanol addition in microcosms containing two sediments collected from the bioremediation test zone at the US Department of Energy Oak Ridge site, TN, USA. One sample was highly bioreduced with ethanol while another was less reduced. Microcosms with the respective sediments were amended with ¹³C labeled ethanol and incubated for 7 days for SIP. Ethanol was rapidly converted to acetate within 24 h accompanied with the reduction of nitrate and sulfate. The accumulation of acetate persisted beyond the 7 d period. Aqueous U did not decline in the microcosm with the reduced sediment due to desorption of U but continuously declined in the less reduced sample. Microbial growth and concomitant ¹³C-DNA production was detected when ethanol was exhausted and abundant acetate had accumulated in both microcosms. This coincided with U(VI) reduction in the less reduced sample. ¹³C originating from ethanol was ultimately utilized for growth, either directly or indirectly, by the dominant microbial community members within 7 days of incubation. The microbial community was comprised predominantly of known denitrifiers, sulfate-reducing bacteria and iron (III) reducing bacteria including Desulfovibrio, Sphingomonas, Ferribacterium, Rhodanobacter, Geothrix, Thiobacillus and others, including the known U(VI)-reducing bacteria Acidovorax, Anaeromyxobacter, Desulfovibrio, Geobacter and Desulfosporosinus. The findings suggest that ethanol biostimulates the U(VI)-reducing microbial community by first serving as an electron donor for nitrate, sulfate, iron (III) and U(VI) reduction, and acetate which then functions as electron donor for U(VI) reduction and carbon source for microbial growth.     

Changes in nutrient content and stable isotope ratios of C and N during decomposition of seagrasses and mangrove leaves along a nutrient availability gradient in Florida Bay,USA

The decomposition of the mangrove Rhizophora mangle and the seagrass Thalassia testudinum was examined using litterbags along a natural gradient in nutrient availability. Seagrass leaves had a higher fraction of their biomass in the labile pool (57%), compared to mangrove leaves (36%) and seagrass rhizomes (29%); the overall decomposition rates of the starting material reflected the fractionation into labile and refractory components. There was no relationship between the N or P content of the starting material and the decomposition rate.

Nutrient availability had no influence on decomposition rate, and mass was lost at the same rate from litterbags that were buried in the sediment and litterbags that were left on the sediment surface. The dynamics of N and P content during decomposition varied as a function of starting material and burial state. N content of decomposing mangrove leaves increased, but seagrass rhizomes decreased in N content during decomposition while there was no change in seagrass leaf N content. These same general patterns held for P content, but buried seagrass leaves increased in P content while surficial leaves decreased. δ¹³C and δ¹⁵N changed by as much as 2‰ during decomposition.     

Influence of haze pollution on water-soluble chemical species in PM2.5 and size-resolved particles at an urban site during fall

To investigate the influence of haze on the chemical composition and formation processes of ambient aerosol particles,PM_(2.5) and size-segregated aerosol particles were collected daily during fall at an urban site of Gwangju,Korea.During the study period,the total concentration of secondary ionic species(SIS) contributed an average of 43.9% to the PM_(2.5) ,whereas the contribution of SIS to the PM_(2.5) during the haze period was 62.3%.The NO_3 and SO~(2-)_4 concentrations in PM_(2.5) during the haze period were highly elevated,being 13.4 and 5.0 times higher than those during non-haze period,respectively.The PM,NO~-_3,SO~(2-)_4,oxalate,water-soluble organic carbon(WSOC),and humic-like substances(HULIS) had tri-modal size distributions peaks at 0.32,1.0,and 5.2 μm during the non-haze and haze periods.However,during the non-haze period they exhibited dominant size distributions at the condensation mode peaking at 0.32 μm,while on October 21 when the heaviest haze event occurred,they had predominant droplet mode size distributions peaking at 1.00 μm.Moreover,strong correlations of WSOC and HULIS with SO~(2-)_4,oxalate,and K+at particle sizes of 1.8 μm indicate that secondary processes and emissions from biomass burning could be responsible for WSOC and HULIS formations.It was found that the factors affecting haze formation could be the local stable synoptic conditions,including the weak surface winds and high surface pressures,the long-range transportation of haze from eastern China and upwind regions of the Korean peninsula,as well as the locally emitted and produced aerosol particles.     

Evaluation of ecological network analysis: Validation of output

Ecological network analysis (ENA) is a modeling approach increasingly being used to evaluate food webs and provide an ecosystem-based approach to resource management. Unfortunately, validation of ENA output is rarely performed. This study represents part of a larger effort to critically evaluate ENA. Here we validate ENA output using stable isotope analysis (SIA), and where validation is not met, determine the effects of modifying trophic networks to reflect validation.     

突发性背景噪声的修正计算分析

噪声测量过程中蝗受背景噪声的影响,而对于突发性背景噪声因其重现性差,实际操作上的“非同时性”给背景噪声的测量结果及修正均带来一些失准问题。为此对突发性背景噪声的校正问题提出初步建议。     

Trace elements and stable isotopes (delta13C and delta15N) in shallow and deep-water organisms from the East China Sea

Trace elements (22) and stable isotope ratios (δ¹⁵N and δ¹³C) were analyzed in marine organisms from shallow (SW) and deep-water (DW) of the East China Sea to understand biomagnification and prey source of trace elements. In the benthic marine organisms from DW, δ¹⁵N values were negatively correlated with Ba, Cu, Ag, Mo, Sr, As, and Co concentrations. This may be due to the specific accumulation in lower trophic animals and/or the biodilution through the food web in DW. Relationships between δ¹⁵N and concentrations of Co, Cr, Bi, and Tl in fish and Ag, Bi, V, Hg, and Tl in crustaceans showed positive correlations, suggesting that trophic position was affecting the concentrations of those elements in phyla, with higher trophic animals retaining higher concentrations than the lower trophic animals. Positive correlations between δ¹³C and Rb were observed in marine organisms. Therefore, Rb may be a possible substitute of δ¹³C as tracer of prey source in the East China Sea although further investigation is required.