Occurrence and distribution of hydrocarbons in the surface microlayer and subsurface water from the urban coastal marine area off Marseilles, Northwestern Mediterranean Sea

Aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dissolved and particulate material from surface microlayer (SML) and subsurface water (SSW) sampled at nearshore observation stations, sewage effluents and harbour sites from Marseilles coastal area (Northwestern Mediterranean) in 2009 and 2010. Dissolved and particulate AH concentrations ranged 0.05–0.41 and 0.04–4.3 μg l⁻¹ in the SSW, peaking up to 38 and 1366 μg l⁻¹ in the SML, respectively. Dissolved and particulate PAHs ranged 1.9–98 and 1.9–21 ng l⁻¹ in the SSW, amounting up 217 and 1597 ng l⁻¹ in the SML, respectively. In harbours, hydrocarbons were concentrated in the SML, with enrichment factors reaching 1138 for particulate AHs. Besides episodic dominance of biogenic and pyrogenic inputs, a moderate anthropisation from petrogenic sources dominated suggesting the impact of shipping traffic and surface runoffs on this urbanised area. Rainfalls increased hydrocarbon concentrations by a factor 1.9–11.5 in the dissolved phase.     

Translation of field tracer-test results into bounding predictions of matrix diffusion in the shallow subsurface at Idaho National Laboratory, USA

Matrix-diffusion parameters deduced from an infiltration tracer test at Idaho National Laboratory (INL), USA, are combined with other site information in an analysis involving two dimensionless lumped parameters to assess the effects of matrix diffusion on contaminant transport at the INL over longer distance and time scales than were evaluated in the test. Matrix diffusion was interrogated in the test by comparing, in three different observation wells, the breakthrough curves of two simultaneously injected nonsorbing solutes that have different diffusion coefficients. The matrix-diffusion parameters deduced from the different breakthrough curves were in good agreement, suggesting that the parameters may be broadly applicable at the INL. With this in mind, the uncertainties in the individual parameters that make up the two lumped parameters were estimated, and the resulting ranges of parameter values were used to assess matrix diffusion over larger scales. Assessments of the effects of flow transients, spatial heterogeneity in transport parameters, and sorption on solute transport in the shallow subsurface flow system were also conducted. The methods presented here should be generally applicable to other settings for making bounding assessments of the effects of matrix diffusion while honoring the information obtained from tracer tests and other supporting data.     

Lake Sediment Core Records of Sulphur Accumulation and Sulphur Isotopic Composition in Central Ontario, Canada Lakes

Stable isotopic compositions and concentrations of total sedimentary sulphur (S) were determined in cores from 6 lakes in the acid-sensitive Muskoka-Haliburton region of south-central Ontario. The isotopic composition of S in deep sediment (> ~ 20 cm) was approximately constant in all lakes, and indicated a pre-industrial δ ³⁴S value between +4.0 and +5.3‰, which is similar to current bulk deposition. Similarly, total S concentrations in deep sediment were relatively low (1.9–5 mg S g⁻¹ dwt) and approximately constant with depth within cores. All lakes exhibited up-core increases in total S and decreases in δ ³⁴S at a depth corresponding to the beginning of industrialization in the Great Lakes region ( ~ 1900), resulting in a generally reciprocal depth pattern between total S concentration and δ ³⁴S ratios. While initial shifts in total S and δ ³⁴S were likely due to enhanced SO₄ reduction of newly available anthropogenic SO₄, both the magnitude and pattern of up-core S enrichment and shifts in δ ³⁴S varied greatly among lakes, and did not match changes in S deposition post 1900. Differences between lakes in total S and δ ³⁴S were not related to any single hydrologic (e.g., residence time) or physical (e.g., catchment-area-to-lake area ratio) lake characteristic. This work indicates that sediment cores do not provide consistent records of changes in post-industrial S deposition in this region, likely due to redox-related mobility of S in upper sediment.     

Tracking the last sea-level cycle: seafloor morphology and shallow stratigraphy of the latest Quaternary New Jersey middle continental shelf

Seafloor geomorphology and surficial stratigraphy of the New Jersey middle continental shelf provide a detailed record of sea-level change during the last advance and retreat of the Laurentide ice sheet (120 kyr B.P. to Present). A NW–SE-oriented corridor on the middle shelf between water depths of 40 m (the mid-shelf “paleo-shore”) and 100 m (the Franklin “paleo-shore”) encompasses 500 line-km of 2D Huntec boomer profiles (500–3500 Hz), an embedded 4.6 km² 3D volume, and a 490 km² swath bathymetry map. We use these data to develop a relative stratigraphy. Core samples from published studies also provide some chronological and sedimentological constraints on the upper <5 m of the stratigraphic succession.The following stratigraphic units and surfaces occur (from bottom to top): (1) “R”, a high-amplitude reflection that separates sediment >46.5 kyr old (by AMS ¹⁴C dating) from overlying sediment wedges; (2) the outer shelf wedge, a marine unit up to 50 m thick that onlaps “R”; (3) “Channels”, a reflection sub-parallel to the seafloor that incises “R”, and appears as a dendritic system of channels in map view; (4) “Channels” fill, the upper portion of which is sampled and known to represent deepening-upward marine sediments 12.3 kyr in age; (5) the “T” horizon, a seismically discontinuous surface that caps “Channels” fill; (6) oblique ridge deposits, coarse-grained shelly units comprised of km-scale, shallow shelf bedforms; and (7) ribbon-floored swales, bathymetric depressions parallel to modern shelf currents that truncate the oblique ridges and cut into surficial deposits.We interpret this succession of features in light of a global eustatic sea-level curve and the consequent migration of the coastline across the middle shelf during the last 120 kyr. The morphology of the New Jersey middle shelf shows a discrete sequence of stratigraphic elements, and reflects the pulsed episodicity of the last sea-level cycle. “R” is a complicated marine/non-marine erosional surface formed during the last regression, while the outer shelf wedge represents a shelf wedge emplaced during a minor glacial retreat before maximum Wisconsin lowstand (i.e., marine oxygen isotope stage 3.1). “Channels” is a widespread fluvial subarial erosion surface formed at the late Wisconsin glacial maximum 22 kyr B.P. The shoreline migrated back across the mid-shelf corridor non-uniformly during the period represented by “Channels” fill. Oblique ridges are relict features on the New Jersey middle shelf, while the ribbon-floored swales represent modern shelf erosion. There is no systematic relationship between modern seafloor morphology and the very shallowly buried stratigraphic succession.     

Mercury’s magnetospheric magnetic field after the first two MESSENGER flybys

The “paraboloid” model of Mercury’s magnetospheric magnetic field is used to determine the best-fit magnetospheric current system and internal dipole parameters from magnetic field measurements taken during the first and second MESSENGER flybys of Mercury on 14 January and 6 October 2008. Together with magnetic field measurements taken during the Mariner 10 flybys on 29 March 1974 and 16 March 1975, there exist three low-latitude traversals separated in longitude and one high-latitude encounter. From our model formulation and fitting procedure a Mercury dipole moment of 196 nT ·  (where R_M is Mercury’s radius) was determined. The dipole is offset from Mercury’s center by 405 km in the northward direction. The dipole inclination to Mercury’s rotation axis is relatively small, ∼4°, with an eastern longitude of 193° for the dipole northern pole. Our model is based on the a priori assumption that the dipole position and the moment orientation and strength do not change in time. The root mean square (rms) deviation between the Mariner 10 and MESSENGER magnetic field measurements and the predictions of our model for all four flybys is 10.7 nT. For each magnetic field component the rms residual is ∼6 nT or about 1.5% of the maximum measured magnetic field, ∼400 nT. This level of agreement is possible only because the magnetospheric current system parameters have been determined separately for each flyby. The magnetospheric stand-off distance, the distance from the planet’s center to the inner edge of the tail current sheet, the tail lobe magnetic flux, and the displacement of the tail current sheet relative to the Mercury solar-magnetospheric equatorial plane have been determined independently for each flyby. The magnetic flux in the tail lobes varied from 3.8 to 5.9 MWb; the subsolar magnetopause stand-off distance from 1.28 to 1.43 R_M; and the distance to the inner edge of the current sheet from 1.23 to 1.32 R_M. The differences in the current systems between the first and second MESSENGER flybys are attributed to the effects of strong magnetic reconnection driven by southward interplanetary magnetic field during the latter flyby.     

Towards evaluating cloud response to climate change using clustering technique identification of cloud regimes

Most of the discrepancies in the climate sensitivity of general circulation models (GCMs) are believed to be due to differences in cloud radiative feedback. Analysis of cloud response to climate change in different ‘regimes’ may offer a more detailed understanding of how the cloud response differs between GCMs. In which case, evaluation of simulated cloud regimes against observations in terms of both their cloud properties and frequency of occurrence will assist in assessing confidence in the cloud response to climate change in a particular GCM. In this study, we use a clustering technique on International Satellite Cloud Climatology Project (ISCCP) data and on ISCCP-like diagnostics from two versions of the Hadley Centre GCM to identify cloud regimes over four different geographical regions. The two versions of the model are evaluated against observational data and their cloud response to climate change compared within the cloud regime framework. It is found that cloud clusters produced by the more recent GCM, HadSM4, compare more favourably with observations than HadSM3. In response to climate change, although the net cloud response over particular regions is often different in the two models, in several instances the same basic processes may be seen to be operating. Overall, both changes in the frequency of occurrence of cloud regimes and changes in the properties (optical depth and cloud top height) of the cloud regimes contribute to the cloud response to climate change.     

Spatial and temporal dynamics of nitrogen exchange in an upwelling reach of a groundwater-fed river and potential response to perturbations changing rainfall patterns under UK climate change scenarios

We report the complex spatial and temporal dynamics of hyporheic exchange flows (HEFs) and nitrogen exchange in an upwelling reach of a 200 m groundwater-fed river. We show how research combining hydrological measurement, geophysics and isotopes, together with nutrient speciation techniques provides insight on nitrogen pathways and transformations that could not have been captured otherwise, including a zone of vertical preferential discharge of nitrate from deeper groundwater, and a zone of rapid denitrification linking the floodplain with the riverbed. Nitrate attenuation in the reach is dominated by denitrification but is spatially highly variable. This variability is driven by groundwater flow pathways and landscape setting, which influences hyporheic flow, residence time and nitrate removal. We observed the spatial connectivity of the river to the riparian zone is important because zones of horizontal preferential discharge supply organic matter from the floodplain and create anoxic riverbed conditions with overlapping zones of nitrification potential and denitrification activity that peaked 10–20 cm below the riverbed. Our data also show that temporal variability in water pathways in the reach is driven by changes in stage of the order of tens of centimetres and by strength of water flux, which may influence the depth of delivery of dissolved organic carbon. The temporal variability is sensitive to changes to river flows under UK climate projections that anticipate a 14%–15% increase in regional median winter rainfall and a 14%–19% reduction in summer rainfall. Superimposed on seasonal projections is more intensive storm activity that will likely lead to a more dynamic and inherently complex (hydrologically and biogeochemically) hyporheic zone. We recorded direct evidence of suppression of upwelling groundwater (flow reversal) during rainfall events. Such flow reversal may fuel riverbed sediments whereby delivery of organic carbon to depth, and higher denitrification rates in HEFs might act in concert to make nitrate removal in the riverbed more efficient.     

Particulate barium fluxes and export production in the northwestern Mediterranean

Biogenic barium, mostly in the barite (BaSO₄) form, has been proposed as a tracer for export production in the ocean. Here we report on biogenic barium (Ba_xs) and particulate organic carbon (POC) fluxes from sediment traps deployed at the DYFAMED site in the Northwestern Mediterranean Sea. Ba_xs fluxes display average values of 37 ± 45 and 50 ± 58 μg/m²/d at 200 and 1000 m respectively, and are linearly correlated to POC fluxes (mean values of 7.9 ± 9.3 and 6.8 ± 6.8 mg C/m²/d at 200 and 1000 m). Export production estimates, calculated using published Ba_xs- or POC-based algorithms, all fall below or close to the lower limit of potential export values proposed in the literature. This work clearly demonstrates the usefulness of Ba_xs as a tracer of oceanic export production in the Northwestern Mediterranean Sea. However, development of a quantitative export production proxy requires a clear understanding of the underlying cause(s) for the observed spatial variations in the relationship between Ba_xs and POC fluxes. The present study confirms that the processes leading to barite formation differ between margin and open-ocean sites and probably account for much of the regional variability in the POC/Ba_xs ratio.     

Modeling Spatially and Temporally Complex Land‐Cover Change: The Case of Western Honduras*

This article presents an econometric analysis of land‐cover change in western Honduras. Ground‐truthed satellite image analysis indicates that between 1987 and 1996 net reforestation occurred in the 1,015‐km² study region. While some reforestation can be attributed to a 1987 ban on logging, the area of reforestation greatly exceeds that of previously clear‐cut areas. Further, new area was also deforested between 1987 and 1996. Thus, the observed land‐cover changes represent a complex mosaic of changing land‐use patterns across time and space. The analysis contributes to the literature on land‐cover change modeling in that: (1) it compares two econometric approaches to capture complex and often bidirectional changes in land cover from 1987 to 1996 as a function of agricultural suitability and transportation costs, and (2) it addresses techniques to identify and correct for spatial autocorrelation in a categorical regression framework.     

The eruptive history of the Tequila volcanic field, western Mexico: ages, volumes, and relative proportions of lava types

The eruptive history of the Tequila volcanic field (1600 km²) in the western Trans-Mexican Volcanic Belt is based on ⁴⁰Ar/³⁹Ar chronology and volume estimates for eruptive units younger than 1 Ma. Ages are reported for 49 volcanic units, including Volcán Tequila (an andesitic stratovolcano) and peripheral domes, flows, and scoria cones. Volumes of volcanic units 1 Ma were obtained with the aid of field mapping, ortho aerial photographs, digital elevation models (DEMs), and ArcGIS software. Between 1120 and 200 kyrs ago, a bimodal distribution of rhyolite (~35 km³) and high-Ti basalt (~39 km³) dominated the volcanic field. Between 685 and 225 kyrs ago, less than 3 km³ of andesite and dacite erupted from more than 15 isolated vents; these lavas are crystal-poor and show little evidence of storage in an upper crustal chamber. Approximately 200 kyr ago, ~31 km³ of andesite erupted to form the stratocone of Volcán Tequila. The phenocryst assemblage of these lavas suggests storage within a chamber at ~2–3 km depth. After a hiatus of ~110 kyrs, ~15 km³ of andesite erupted along the W and SE flanks of Volcán Tequila at ~90 ka, most likely from a second, discrete magma chamber located at ~5–6 km depth. The youngest volcanic feature (~60 ka) is the small andesitic volcano Cerro Tomasillo (~2 km³). Over the last 1 Myr, a total of 128±22 km³ of lava erupted in the Tequila volcanic field, leading to an average eruption rate of ~0.13 km³/kyr. This volume erupted over ~1600 km², leading to an average lava accumulation rate of ~8 cm/kyr. The relative proportions of lava types are ~22–43% basalt, ~0.4–1% basaltic andesite, ~29–54% andesite, ~2–3% dacite, and ~18–40% rhyolite. On the basis of eruptive sequence, proportions of lava types, phenocryst assemblages, textures, and chemical composition, the lavas do not reflect the differentiation of a single (or only a few) parental liquids in a long-lived magma chamber. The rhyolites are geochemically diverse and were likely formed by episodic partial melting of upper crustal rocks in response to emplacement of basalts. There are no examples of mingled rhyolitic and basaltic magmas. Whatever mechanism is invoked to explain the generation of andesite at the Tequila volcanic field, it must be consistent with a dominantly bimodal distribution of high-Ti basalt and rhyolite for an 800 kyr interval beginning ~1 Ma, which abruptly switched to punctuated bursts of predominantly andesitic volcanism over the last 200 kyrs.Electronic Supplementary Material Supplementary material is available in the online version of this article at Editorial responsility: J. Donnelly-NolanThis revised version was published online in January 2005 with corrections to Tables 1 and 3.An erratum to this article can be found at