Atmospheric mercury near Salmon Falls Creek Reservoir in southern Idaho

Gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) were measured over 2-week seasonal field campaigns near Salmon Falls Creek Reservoir in south-central Idaho from the summer of 2005 through the fall of 2006 and over the entire summer of 2006 using automated Tekran Hg analyzers. GEM, RGM, and particulate Hg (HgP) were also measured at a secondary site 90 km to the west in southwestern Idaho during the summer of 2006. The study was performed to characterize Hg air concentrations in the southern Idaho area for the first time, estimate Hg dry deposition rates, and investigate the source of observed elevated concentrations. High seasonal variability was observed with the highest GEM (1.91 ± 0.9 ng m⁻³) and RGM (8.1 ± 5.6 pg m⁻³) concentrations occurring in the summer and lower values in the winter (1.32 ± 0.3 ng m⁻³, 3.2 ± 2.9 pg m⁻³ for GEM, RGM, respectively). The summer-average HgP concentrations were generally below detection limit (0.6 ± 1 pg m⁻³). Seasonally averaged deposition velocities calculated using a resistance model were 0.034 ± 0.032, 0.043 ± 0.040, 0.00084 ± 0.0017 and 0.00036 ± 0.0011 cm s⁻¹ for GEM (spring, summer, fall and winter, respectively) and 0.50 ± 0.39, 0.40 ± 0.31, 0.51 ± 0.43 and 0.76 ± 0.57 cm s⁻¹ for RGM. The total annual RGM + GEM dry deposition estimate was calculated to be 11.9 ± 3.3 μg m⁻², or about 2/3 of the total (wet + dry) deposition estimate for the area. Periodic elevated short-term GEM (2.2–12 ng m⁻³) and RGM (50–150 pg m⁻³) events were observed primarily during the warm seasons. Back-trajectory modeling and PSCF analysis indicate predominant source directions to the SE (western Utah, northeastern Nevada) and SW (north-central Nevada) with fewer inputs from the NW (southeastern Oregon and southwestern Idaho).     

Total particulate and reactive gaseous mercury in ambient air on the eastern slope of the Mt. Gongga area,China

Total particulate mercury (TPM) and reactive gaseous mercury (RGM) concentrations in ambient air on the eastern slope of the Mt. Gongga area, Sichuan Province, Southwestern China were monitored from 25 May, 2005 to 29 April, 2006. Simultaneously, Hg concentrations in rain samples were measured from January to December, 2006. The average TPM and RGM concentrations in the study site were 30.7 and 6.2 pg m⁻³, which are comparable to values observed in remote areas in Northern America and Europe, but much lower than those reported in some urban areas in China. The mean seasonal RGM concentration was slightly higher in spring (8.0 pg m⁻³) while the minimum mean concentration was observed in winter (4.0 pg m⁻³). TPM concentrations ranged across two orders of magnitude from 5.2 to 135.7 pg m⁻³ and had a clear seasonal variation: winter (74.1 pg m⁻³), autumn (22.5 pg m⁻³), spring (15.3 pg m⁻³) and summer (10.8 pg m⁻³), listed in decreasing order. The annual wet deposition was 9.1 μg m⁻² and wet deposition in the rainy season (May–October) represented over 80% of the annual total. The temporal distribution of TPM and RGM suggested distinguishable dispersion characteristics of these Hg species on a regional scale. Elevated TPM concentration in winter was probably due to regional and local enhanced coal burning and low wet deposition velocity. The RGM distribution pattern is closely related to daily variation in UV radiation observed during the winter sampling period indicating that photo-oxidation processes and diurnal changes in meteorology play an important role in RGM generation.     

U-Th systematics and Th ages of carbonate chimneys at the Lost City Hydrothermal Field

The Lost City Hydrothermal Field (LCHF) is a serpentinite-hosted vent field located 15 km west of the spreading axis of the Mid-Atlantic Ridge. In this study, uranium-thorium (U-Th) geochronological techniques have been used to examine the U-Th systematics of hydrothermal fluids and the ²³⁰Th ages of hydrothermally-precipitated carbonate chimneys at the LCHF. Fluid sample analyses indicate that endmember fluids likely contain only 0.0073 ng/g U or less compared to 3.28 ± 0.03 ng/g of U in ambient seawater. For fluid samples containing only 2-21% ambient seawater (1.1-11 mmol/kg Mg), Th concentration is 0.11-0.13 pg/g and surrounding seawater concentrations average 0.133 ± 0.016 pg/g. The ²³⁰Th/²³²Th atomic ratios of the vent fluids range from 1 (±10) × 10⁻⁶ to 11 (±5) × 10⁻⁶, are less than those of seawater, and indicate that the vent fluids may contribute a minor amount of non-radiogenic ²³⁰Th to the LCHF carbonate chimney deposits. Chimney ²³⁸U concentrations range from 1 to 10 μg/g and the average chimney corrected initial δ²³⁴U is 147.2 ± 0.8, which is not significantly different from the ambient seawater value of 146.5 ± 0.6. Carbonate ²³²Th concentrations range broadly from 0.0038 ± 0.0003 to 125 ± 16 ng/g and ²³⁰Th/²³²Th atomic ratios vary from near seawater values of 43 (±8) × 10⁻⁶ up to 530 (±25) × 10⁻³. Chimney ages, corrected for initial ²³⁰Th, range from 17 ± 6 yrs to 120 ± 13 kyrs. The youngest chimneys are at the intersection of two active, steeply-dipping normal faults that cut the Atlantis Massif; the oldest chimneys are located in the southwest portion of the field. Vent deposits on a steep, fault-bounded wall on the east side of the field are all <4 kyrs old, indicating that mass wasting in this region is relatively recent. Comparison of results to prior age-dating investigations of submarine hydrothermal systems shows that the LCHF is the most long-lived hydrothermal system known to date. It is likely that seismic activity and active faulting within the Atlantis Massif and the Atlantis Fracture Zone, coupled with volumetric expansion of the underlying serpentinized host rocks play major roles in sustaining hydrothermal activity at this site. The longevity of venting at the LCHF may have implications for ecological succession of microorganisms within serpentinite-hosted vent environments.     

Mercury fluxes from air/surface interfaces in paddy field and dry land

In order to provide insight into the characteristics of Hg exchange in soil/water-air surface from cropland (including paddy field and dry land), Hg fluxes were measured in Chengjiang. Mercury fluxes were measured using the dynamic flux chamber method, coupled with a Lumex® multifunctional Hg analyzer RA-915⁺ (Lumex Ltd., Russia). The Hg fluxes from paddy field and dry land were alternatively measured every 30 min. Data were collected for 24-48 h once per month for 5 months. Mercury fluxes in both fields were synchronously measured under the same conditions to compare Hg emissions between paddy field and dry land over diurnal and seasonal periods and find out what factors affect Hg emission on each surface. These results indicated that air Hg concentrations at the monitoring site was double the value observed at the global background sites in Europe and North America. The Hg release fluxes were 46.5 ± 22.8 ng m⁻² h⁻¹ in the warm season, 15.5 ± 18.8 ng m⁻² h⁻¹ in the cold season for dry land, and 23.8 ± 15.6 ng m⁻² h⁻¹ in the warm season, 6.3 ± 11.9 ng m⁻² h⁻¹ in the cold season for paddy field. Solar radiation is important in the emission of Hg over both sites. Hg exchange at the soil/air and water/air interfaces showed temporal variations. The amount of Hg emission from dry land was higher than that from the paddy field, and the emission in daytime was higher than that at night. Moreover, Hg emissions from land covered by crops, was lower than that for bare land.     

Variation of initial Th/Th and limits of high precision U-Th dating of shallow-water corals

One hundred eighty U-Th data, including 23 isochrons on 24 pristine modern and Holocene corals and 33 seawater samples, were analyzed using sector-field mass spectrometry to understand the variability of initial ²³⁰Th/²³²Th (²³⁰Th/²³²Th₀). This dataset allows us to further assess the accuracy and precision of coral ²³⁰Th dating method. By applying quality control, including careful sampling and subsampling protocols and the use of contamination-free storage and workbench spaces, the resulting low procedural blanks give an equivalent uncertainty in age of only ±0.2-0.3 yr for 1-2 g of coral sample. Using site-specific ²³⁰Th/²³²Th₀ values or isochron techniques, our study demonstrates that corals with an age less than 100 yrs can be ²³⁰Th-dated with precisions of ±1 yr. Six living subtidal coral samples were collected from two continental shelf sites, Nanwan off southern Taiwan in the western Pacific and Son Tra off central Vietnam in the South China Sea; one coral core was drilled from an open-ocean site, Santo Island, Vanuatu, in the western tropical Pacific; and modern and fossil intertidal coral slabs, 17 in total, were cut from six sites around the islands of Simeulue, Lago, North Pagai and South Pagai of Sumatra in the eastern Indian Ocean. The results indicate that the main source of thorium is the dissolved phase of seawater, with variation of ²³⁰Th/²³²Th₀ depending on local hydrology. With intense input of terrestrial material, low ²³⁰Th/²³²Th₀ atomic ratios of 4.9 × 10⁻⁶ and 3.2 × 10⁻⁶ with a 10% variation are observed in Nanwan and Son Tra, respectively. At the Santo site, we find a value of 5.6 × 10⁻⁶ at 4 horizons and one high value of 24 × 10⁻⁶ in a sample from AD 1974.6 ± 0.5, likely due to the upwelling of cold water during a La Niña event between AD 1973 and 1976. The natural dynamics of ²³⁰Th/²³²Th₀ recorded in the intertidal corals at sites in the Sumatran islands are complicated so that this value varies significantly from 3.0 to 9.4 × 10⁻⁶. Three of the 141 modern coral ²³⁰Th ages differ from their true ages by −23 to +4, indicating the presence of detrital material with anomalous ²³⁰Th/²³²Th values. Duplicate measurement of coeval subsamples is therefore recommended to verify the age accuracy. This improved high precision coral ²³⁰Th dating method raises the prospects of refining the age models for band-counted and tracer-tuned chronologies and of advancing coral paleoclimate research.     

An iodine mass-balance for Lake Constance, Germany: Insights into iodine speciation changes and fluxes

Lake Constance is one of Europe’s largest oligotrophic lakes and provides a water source for more than 4.5 million people in Germany and Switzerland. We present here a 12 month study on iodine concentrations, speciation and fluxes to and from the lake to gain a quantitative understanding of the limnic iodine cycle. Monthly water samples were obtained from all major tributaries (14) and the outflow to construct a mass-balance model. Sediment traps were also deployed in the lake for two years at two different stations. Total soluble iodine (TSI) in aqueous samples were analysed by ICP-MS and speciation (iodide, iodate and soluble organically bound iodine, SOI) by ion chromatography-ICP-MS. Iodine concentrations in the Alpine tributaries (1-2 μg l⁻¹) decreased over the summer months due to increasing proportions of snow and glacial melt water from the Alps, while iodine levels in the lowland rivers (∼2-10 μg l⁻¹) increased over the summer. Deposition of TSI to the catchment (16,340 kg I yr⁻¹) was similar to the TSI out-flux by rivers (16,000 kg I yr⁻¹). By also including the particulate riverine iodine flux out of the catchment (∼12,350 kg I yr⁻¹) it is shown that the catchment is a net source of iodine, with the highest particulate fluxes coming from the Alpine rivers. The total TSI flux to the lake was 16,770 kg I yr⁻¹, the largest proportion coming from the Alpenrhein (43%), followed by the Schussen (8%) and Bregenzer Ach (7.7%). Overall the mass-balance for TSI in the lake was negative, with more iodine flowing out of the lake than in (−2050 kg I yr⁻¹; 12% of TSI in-flux). To maintain mass-balance, 8.8 μg I m⁻² d⁻¹ from the Obersee and 23 μg I m⁻² d⁻¹ from the Untersee must be released from the sediments into the water column. Thus, in comparison with the total iodine flux to the sediments measured by the sediment traps (4762-8075 kg I yr⁻¹), up to 39% of the deposited iodine may be mobilised back into the lake. SOI was the dominant iodine fraction entering the lake, with a total flux of 10,290 kg I yr⁻¹ (64% of TSI input), followed by iodate (3120 kg I yr⁻¹) and iodide (2760 kg I yr⁻¹). Net formation of SOI from iodide and iodate was also noted within the lake, with an estimated production of 6560 kg I yr⁻¹, suggesting a strong role for biology in iodine cycling. In conclusion, organically bound iodine was the dominant iodine species in aqueous and solid phases in Lake Constance, despite low DOC concentrations (<2 mg l⁻¹), and thus is expected to play an important role in iodine cycling in most freshwater environments.     

Hydrogeological and geochemical control of the variations of Rn concentrations in a hard rock aquifer: Insights into the possible role of fracture-matrix exchanges

To investigate the possible variations of Rn concentration in crystalline rocks as a function of flow conditions, a field study was carried out of a fractured aquifer in granite. The method is based on the in situ measurement of Rn in groundwater, aquifer tests for the determination of hydraulic characteristics of the aquifer and laboratory measurement of Rn exhalation rate from rocks. A simple crack model that simulates the Rn concentration in waters circulating in a fracture intersecting a borehole was also tested. The Rn concentrations in groundwaters from boreholes of the study site ranged from 192 to 1597 Bq L⁻¹. The Rn exhalation rates of selected samples of granite and micaschist were determined from laboratory experiments. The results yielded fluxes varying from 0.5 to 1.3 mBq m⁻² s⁻¹ in granite and from 0.5 to 0.9 mBq m⁻² s⁻¹ in micaschists. Pumping tests were performed in the studied boreholes to estimate the transmissivity and calculate the equivalent hydraulic aperture of the fractures. Transmissivities ranged from 10⁻⁵ to 10⁻³ m² s⁻¹. Using the cubic law, hydraulic equivalent fracture apertures were calculated to be in the range of 0.5–2.3 mm.     

Bromine species fluxes from Lake Constance’s catchment, and a preliminary lake mass balance

Bromine was historically termed a cyclic salt in terrestrial freshwater environments due to its perceived conservative cycling between the oceans and the continents. This basic assumption has been challenged recently, with evidence that bromine is involved in dynamic chemical cycles in soils and freshwaters. We present here a study on dissolved bromine species (bromide, organically bound bromine, DOBr) concentrations and fluxes as well as sediment trap bromine levels and fluxes in Lake Constance, a large lake in southern Germany. Water samples were obtained from all major and some minor inflows and outflows over one year, where-after dissolved bromine species were measured by a combination of ICP-MS and ion chromatography coupled to an ICP-MS (IC-ICP-MS). Sediment traps were deployed at two locations for two years with Br, Ti and Zr levels being measured by μ-XRF.190 t yr⁻¹ of total dissolved bromine (TDBr) was delivered to the lake via 14 rivers and precipitation, with the rivers Alpenrhein (84 t TDBr yr⁻¹) and the Schussen (50 t TDBr yr⁻¹) providing the largest sources. The estimated particulate bromine flux contributed an extra 24-26 t Br yr⁻¹. In comparison, only 40 t TDBr yr⁻¹ was deposited to the lake’s catchment by precipitation, and thus ∼80% of the riverine TDBr flux came from soils and rocks. Bromide was the dominant species accounting for, on average, 78% of TDBr concentrations and 93% of TDBr flux to the lake. Despite some high concentrations in the smaller lowland rivers, DOBr was only a minor component of the total riverine bromine flux (∼12 t yr⁻¹, 7%), most of which came from the rivers Schussen, Bregenzer Ach and Argen. In contrast, most of the bromine in the sediment traps was bound to organic matter, and showed a clear seasonal pattern in concentrations, with a maximum in winter and minimum in summer. The summer minimum is thought to be due to dilution of a high Br autochthonous component by low bromine mineral and organic material from the catchment, which is supported by Ti, Zr and Br/C_org data. In the lake bromine was irreversibly lost to the sediments, with best flux estimates based on mass-balance and sediment trap data of +50-90 μg Br m⁻² d⁻¹. Overall, it appears that bromine is not simply a cyclic salt in the case of Lake Constance, with a clear geological component and dynamic lacustrine biogeochemistry.     

Pathways and regulation of carbon, sulfur and energy transfer in marine sediments overlying methane gas hydrates on the Opouawe Bank (New Zealand)

This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr⁻¹. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m⁻² d⁻¹, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m⁻² d⁻¹ of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m⁻² d⁻¹ of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m⁻² d⁻¹ to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m⁻² d⁻¹ of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100-200 nmol cm⁻³ d⁻¹). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m⁻² d⁻¹ or 96 mW m⁻² of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide oxidation and anaerobic oxidation of methane (AOM) produce 95% and 2% of this energy flux, respectively. The low power output by AOM is due to strong bioenergetic constraints imposed on the reaction rate by the composition of the chemical environment. These constraints provide a high potential for dissolved methane efflux from the sediment (12.0 mmol m⁻² d⁻¹) and indicates a much lower efficiency of (dissolved) methane sequestration by AOM at seeps than considered previously. Nonetheless, AOM is able to consume a third of the ascending methane flux (5.9 mmol m⁻² d⁻¹ of CH₄) with a high efficiency of energy expenditure (35 mmol CH₄ kJ⁻¹). It is further proposed that bioenergetic limitation of AOM provides an explanation for the non-zero sulfate concentrations below the AOM zone observed here and in other active and passive margin sediments.     

The continental shelf benthic iron flux and its isotope composition

Benthic iron fluxes from sites along the Oregon-California continental shelf determined using in situ benthic chambers, range from less than 10 μmol m⁻² d⁻¹ to values in excess of ∼300 μmol m⁻² d⁻¹. These fluxes are generally greater than previously published iron fluxes for continental shelves contiguous with the open ocean (as opposed to marginal seas, bays, or estuaries) with the highest fluxes measured in the regions around the high-sediment discharge Eel River and the Umpqua River. These benthic iron fluxes do not covary with organic carbon oxidation rates in any systematic fashion, but rather seem to respond to variations in bottom water oxygen and benthic oxygen demand. We hypothesize that the highest rates of benthic iron efflux are driven, in part, by the greater availability of reactive iron deposited along these river systems as compared to other more typical continental margin settings. Bioirrigation likely plays an important role in the benthic Fe flux in these systems as well. However, the influence of bottom water oxygen concentrations on the iron flux is significant, and there appears to be a threshold in dissolved oxygen (∼60-80 μM), below which sediment-ocean iron exchange is enhanced. The isotope composition of this shelf-derived benthic iron is enriched in the lighter isotopes, and appears to change by ∼3‰ (δ⁵⁶Fe) during the course of a benthic chamber experiment with a mean isotope composition of −2.7 ± 1.1‰ (2 SD, n = 9) by the end of the experiment. This average value is slightly heavier than those from two high benthic Fe flux restricted basins from the California Borderland region where δ⁵⁶Fe is −3.4 ± 0.4‰ (2 SD, n = 3). These light iron isotope compositions support previous ideas, based on sediment porewater analyses, suggesting that sedimentary iron reduction fractionates iron isotopes and produces an isotopically light iron pool that is transferred to the ocean water column. In sum, our data suggest that continental shelves may export a higher efflux of iron than previously hypothesized, with the likelihood that along river-dominated margins, the benthic iron flux could well be orders of magnitude larger than non-river dominated shelves. The close proximity of the continental shelf benthos to the productive surface ocean means that this flux is likely to be essential for maintaining ecosystem micronutrient supply.     

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field,Taupo Volcanic Zone,New Zealand

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW_e). Soil CO₂ degassing was quantified with 2663 CO₂ flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m⁻²) using published soil temperature heat flow functions. Both CO₂ flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO₂ gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO₂ emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO₂ emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO₂ emissions due to the loss of >99% of the original CO₂ content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO₂ release to the atmosphere from the high temperature reservoir at Ohaaki. The CO₂ flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO₂ flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m⁻² d⁻¹) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO₂ diffuses through porous media of the soil zone. For high-flux sites (>300 g m⁻² d⁻¹), the δ¹³CO₂ signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO₂ source for each respective upflow. Flux thresholds of <30 g m⁻² d⁻¹ for purely diffusive gas transport, between 30 and 300 g m⁻² d⁻¹ for combined diffusive–advective transport, and ?300 g m⁻² d⁻¹ for purely advective gas transport at Ohaaki were assigned. δ¹³CO₂ values and cumulative probability plots of CO₂ flux data both identified a threshold of ∼15 g m⁻² d⁻¹ by which background (atmospheric and soil respired) CO₂ may be differentiated from hydrothermal CO₂.     

Temporal variability in terrestrially-derived sources of particulate organic carbon in the lower Mississippi River and its upper tributaries

In this study, we examined the temporal changes of terrestrially-derived particulate organic carbon (POC) in the lower Mississippi River (MR) and in a very limited account, the upper tributaries (Upper MR, Ohio River, and Missouri River). We used for the first time a combination of lignin-phenols, bulk stable carbon isotopes, and compound-specific isotope analyses (CSIA) to examine POC in the lower MR and upper tributaries.A lack of correlation between POC and lignin phenol abundances (Λ₈) was likely due to dilution effects from autochthonous production in the river, which has been shown to be considerably higher than previously expected. The range of δ¹³C values for p-hydroxycinnamic and ferulic acids in POC in the lower river do support that POM in the lower river does have a significant component of C₄ in addition to C₃ source materials. A strong correlation between δ¹³C values of p-hydroxycinnamic, ferulic, and vanillyl phenols suggests a consistent input of C₃ and C₄ carbon to POC lignin while a lack of correlation between these same phenols and POC bulk δ¹³C further indicates the considerable role of autochthonous carbon in the lower MR POC budget. Our estimates indicate an annual flux of POC of 9.3 × 10⁸ kg y⁻¹ to the Gulf of Mexico. Total lignin fluxes, based on Λ₈ values of POC, were estimated to be 1.2 × 10⁵ kg y⁻¹. If we include the total dissolved organic carbon (DOC) flux (3.1 × 10⁹ kg y⁻¹) reported by [Bianchi T. S., Filley T., Dria K. and Hatcher, P. (2004) Temporal variability in sources of dissolved organic carbon in the lower Mississippi River. Geochim. Cosmochim. Acta68, 959-967.], we get a total organic carbon flux of 4.0 × 10⁹ kg y⁻¹. This represents 0.82% of the annual total organic carbon supplied to the oceans by rivers (4.9 × 10¹¹ kg).     

Radon transfer from groundwater used in showers to indoor air

Estimation of Rn transfer from water to indoor air based on multi-day measurements may underestimate alpha exposure that occurs at short time scales in confined spaces, such as from showering, in houses with high Rn activities in the water supply. In order to examine one such incremental increase in exposure, variations in Rn in water and indoor air in 18 houses with private wells in western North Carolina (USA) were investigated. Radon in well water ranged from 158 to 811 Bq L⁻¹ (median 239 Bq L⁻¹). After 20-min showers in bathrooms with closed doors, peak Rn in air increases (above background) ranged from 71 to 4420 Bq m⁻³ (median 1170 Bq m⁻³). Calculated transfer coefficients at the scale of a 40-min closed bathroom (20-min shower plus 20 min post-shower) are described by a lognormal distribution whose geometric mean exceeds the widely-used ∼10⁻⁴ whole-house transfer coefficient by about one order of magnitude. As short-lived decay products grow from shower-derived Rn, short-term alpha energy exposure occurs in bathrooms in addition to the exposure caused by Rn mixed throughout the volume of the house. Due to the increasing ratio of Rn decay products to Rn, alpha energy exposure is greatest several minutes after the shower is turned off. For a 7.2-min shower with 10 min of additional exposure before opening the door, a geometric mean 5.6% increase in exposure over the ∼10⁻⁴ whole-house transfer coefficient derived from longer measurement periods was estimated. In addition to Rn activity in water, short-term shower exposure to Rn progeny depends on exposure time, ventilation, attachment and deposition, among other variable factors that characterize individual houses and residents.     

Methane microseepage from different sectors of the Yakela condensed gas field in Tarim Basin,Xinjiang, China

Methane microseepage is the result of natural gas migration from subsurface hydrocarbon accumulations to the Earth’s surface, and it is quite common in commercial petroleum fields. While the role of microseepage as a pathfinder in petroleum exploration has been known for about 80 a, its significance as an atmospheric CH₄ source has only recently been studied, and flux data are currently available only in the USA and Europe. With the aim of increasing the global data-set and better understanding flux magnitudes and variabilities, microseepage is now being extensively studied in China. A static flux chamber method was recently applied to study microseepage emissions into the atmosphere in four different sectors of the Yakela condensed gas field in Tarim Basin, Xinjiang, China, and specifically in: (a) a faulted sector, across the Luntai fault systems; (b) an oil–water interface sector, at the northern margin of the field; (c) an oil–gas interface sector, in the middle of the field; (d) an external area, outside the northern gas field boundaries. The results show that positive CH₄ fluxes are pervasive in all sectors and therefore, only part of the CH₄ migrating from the deep oil–gas reservoirs is consumed in the soil by methanotrophic oxidation. The intensity of gas seepage seems to be controlled by subsurface geologic settings and lateral variabilities of natural gas pressure in the condensed gas field. The highest CH₄ fluxes, up to ∼14 mg m⁻² d⁻¹ (mean of 7.55 mg m⁻² d⁻¹) with higher spatial variability (standard deviation, σ: 2.58 mg m⁻² d⁻¹), occur in the Luntai fault sector. Merhane flux was lower in the oil–water area (mean of 0.53 mg m⁻² d⁻¹) and the external area (mean of 1.55 mg m⁻² d⁻¹), and at the intermediate level in the gas–oil sector (mean of 2.89 mg m⁻² d⁻¹). These values are consistent with microseepage data reported for petroleum basins in the USA and Europe. The build-up of methane concentration in the flux chambers is always coupled with an enrichment of ¹³C, from δ¹³C₁ of −46‰ to −42.5‰ (VPDB), which demonstrates that seeping methane is thermogenic, as that occurring in the deep Yakela reservoir. Daily variations of microseepage are very low, with minima in the afternoon, corresponding to higher soil temperature (and higher methanotrophic consumption), and maxima in the early morning (when soil temperatures are lowest). A preliminary and rough estimate of the total amount of CH₄ exhaled from the Yakela field is in the order of 10² tonnes a⁻¹.     

Pore-water response on seasonal environmental changes in intertidal sediments of the Weser Estuary,Germany

In order to determine time-dependent changes in estuarine pore-water chemistry and flux variations across the sediment-water interface, sediment cores of an intertidal mud flat in the Weser Estuary were taken monthly over a one-year period. Sediment temperature, pH, Eh, Cl^–, O₂, NO ₃ ^– , and SO ₄ ^2– pore-water concentrations were measured and showed variations that relate to the changes of surface temperature and estuarine water composition. Fick's first law was applied to quantify diffusive fluxes from concentration gradients in the diffusive boundary layer and in the pore water. Total nitrate fluxes were calculated from flux chamber experiments. Diffusive oxygen fluxes increased from 5 mmol m^–2 d^–1 in winter to 18 mmol m^–2 d^–1 in early summer, while nitrate fluxes into the sediment increased from 3 mmol m^–2 d^–1 in winter to 60 mmol m^–2 d^–1 in early summer. Oxygen and nitrate fluxes into the sediment correlated linearly to sediment temperature. Sulfate fluxes increased from 0.5 mmol m^–2 d^–1 in winter to 10 mmol m^–2 d^–1 in August and September. Converted into carbon fluxes, the sum of these oxidants ranged from 10 mmol m^–2 d^–1 in winter to 80 mmol m^–2 d^–1 in summer. An estimation of the upper limit of the annual nitrate flux into the sediment showed that about 10% of the 250,000 t of nitrate discharged annually by the river may be decomposed within the inner Weser Estuary.     

Characterization and cycling of atmospheric mercury along the central US Gulf Coast

Concentrations of atmospheric Hg species, elemental Hg (Hg^°), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM_2.5) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m⁻³, 4.0 ± 7.5 pg m⁻³ and 2.7 ± 3.4 pg m⁻³, respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m⁻³), but not for Hg^° or Hg-PM_2.5. Elevated RGM concentrations (>25 pg m⁻³) in April and May of 2005 correlated with elevated average daytime O₃ concentrations (>55 ppbv) and high light intensity (>500 W m⁻²). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly (p < 0.05) with peaks in SO₂ concentration and corresponded to periods of high light intensity and lower average daytime O₃ concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg^° by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM.     

Sedimentation of particulate matter in the Dona Paula Bay, West Coast of India during November to May 1995–1997

Data on hydrography, nutrients, suspended particles, and sedimented particles were collected at weekly intervals from November to May during 1995 to 1997 at a station in the coastal waters of Dona Paula Bay, India. Suspended and sedimented particles were analyzed for total suspended matter (SPM), total sedimented particulate matter (TPM), particulate organic carbon (POC), particulate organic nitrogen (PON), chlorophylla (chla), and diatom abundance. Variations in hydrography and nutrients influenced the quantity and composition of sedimented particles. The TPM, POC, PON, and chla fluxes showed small-scale seasonal variations and were higher in the summer (February to May) than in the winter (November to January). Resuspension of carbon accounted for approximately 25% of the gross POC and was highest in April 1997 (45%). The mean net POC flux was 197±90 mg C m⁻² d⁻¹ and accounts for 4.6% of the TPM. The average C∶N (w∶w) ratio of the sedimented material was 13.2±6.6. The POC:chla ratio was relatively higher in the sedimented material as compared to the suspended material. The particulate carbon reaching the bottom sediment was 39% of the primary production. The low organic carbon concentration (approximately 0.1% of dry sediment) in the sediments implies that about 98% of the sedimented carbon was either consumed at the sedimentwater interface or resuspended/advected before it was finally buried into the sediments.     

Mercury emission from terrestrial background surfaces in the eastern USA. Part I: Air/surface exchange of mercury within a southeastern deciduous forest (Tennessee) over one year

This study focused on the development of a seasonal data set of the Hg air/surface exchange over soils associated with low Hg containing surfaces in a deciduous forest in the southern USA. Data were collected every month for 11 months in 2004 within Standing Stone State Forest in Tennessee using the dynamic flux chamber method. Mercury air/surface exchange associated with the litter covered forest floor was very low with the annual mean daytime flux being 0.4 ± 0.5 ng m⁻² h⁻¹ (n = 301). The daytime Hg air/surface exchange over the year oscillated between emission (81% of samples with positive flux) and deposition (19% of samples with negative flux). A seasonal trend of lower emission in the spring and summer (closed canopy) relative to the fall and winter (open canopy) was observed. Correlations were found between the air/surface exchange and certain environmental factors on specific days sampled but not collectively over the entire year. The very low magnitude of Hg air/surface exchange as observed in this study suggests that an improved methodology for determining and reporting emission fluxes is needed when the values of fluxes and chamber blanks are both very low and comparable. This study raises questions and points to a need for more research regarding how to scale the Hg air/surface exchange for surfaces with very low emissions.     

Scavenging and particle residence times determined from 234Th/238U disequilibria in the coastal waters of Mecklenburg Bay

Activities of the naturally occurring radionuclide ²³⁴Th were determined in water samples of Mecklenburg Bay (SW Baltic Sea) using a new Th-specific diatomite adsorption technique followed by liquid scintillation spectrometry. Activities of “dissolved” (operationally defined as Th in the centrifugate) and particulate ²³⁴Th varied in the range of 1.4–6.9 and 0.9–9.3 mBq l⁻¹, respectively. A significant correlation between K_d and SPM concentration was found. From this particle-concentration effect, the “colloidal pumping” model predicts that 98% of the “dissolved” Th is associated with colloids rather than being truly dissolved. Relative to calculated activities of the parent nuclide ²³⁸U in the Bay, the ²³⁴Th data yielded mean ²³⁴Th scavenging residence times in the range of 1.2–9.7 days. Particulate ²³⁴Th activities are inversely correlated to SPM concentrations. Particle residence times ranged from a few days in winter up to 20 days in spring characterized by less intense bottom currents. The hydrodynamic regime is the master variable controlling scavenging of Th and other similarly particle-reactive elements in Mecklenburg Bay.     

Phytoplankton and particulate matter in Carlingford Lough, Ireland: An assessment of food availability and the impact of bivalve culture

In an attempt to assess the impact of bivalve culture in Carlingford Lough, Ireland, the seasonal cycles of nutrients, particulate matter, chlorophylla, and phytoplankton in the lough was investigated in 1992. Chlorophyll levels showed an increase in April, corresponding to the annual spring bloom, and levels remained relatively high (2–12 mg m^?3) throughout the summer before dropping to a winter minimum by December. Throughout the summer the phytoplankton community was dominated by diatoms, with microflagellates becoming an increasingly larger fraction of the biomass in autumn and winter. Dinoflagellates were only present on occasion in low numbers during the summer months. Seasonal variations in nitrate, phosphate, and silicate concentrations at all stations showed characteristic winter maxima and summer minima. Nitrate concentrations had reached a minimum undetectable level by June, at a time when the main freshwater input from the Clanrye River had dropped to <0.3 m³ s^?1. Particulate organic carbon (POC) composed approximately 5% of the suspended matter, with highest values in winter due to resuspension. Levels of biologically available POC, as determined by a modified BOD technique, were greatest in summer, and an inverse relationship was observed between total POC and its fraction that was biologically available. Most of the labile fraction was considered to be phytoplankton, and remineralization during the summer is suggested as a mechanism for maintaining high productivity during the summer months. Although the phytoplankton biology was uncoupled with that outside the lough, it is concluded that there is scope for expansion of the local bivalve mariculture industry without altering the ecosystem of the lough. The upper limit on such expansion would be set by practical considerations such as availability of space and site suitability due to water quality.