Ultraminiature X-ray fluorescence spectrometer for in-situ geochemical analysis on Mars

Determination of the surface composition at various sites on the planet Mars will provide information essential to a better understanding of the geologic history of this complex planet. A spectrometer based upon the X-ray fluorescence method of elemental analysis has been developed in an ultraminiature, rugged form suitable for a spacecraft mission to Mars. The instrument employs two radioisotope sources (⁵⁵Fe and¹⁰⁹Cd) which irradiate adjacent areas on a regolith sample. Fluorescent X-rays emitted by the sample are detected by four thin-window proportional counters. Using pulse-height discrimination, the energy spectra are determined. Virtually all elements above sodium in the periodic table are detected if present at sufficient levels. Minimum detection limits range from 30 ppm to 2%. depending upon the element and the matrix. For most elements, they are below 0.5%. Accuracies also depend upon the matrix, but are generally better than ± 0.5% for all elements of atomic number greater than 14. Elements below sodium are also detected, but as a single group. Ambiguities of identification of the elements producing the observed spectra are minimal. Exotic geological materials are, therefore, just as susceptible to analysis as are the more common rocks. A computer model of the instrument has been developed and tested. This model was used to optimize instrument parameters during the design phase, and has now been expanded to perform automatic analysis of the output data.     

Bioremediation of petroleum hydrocarbons in anoxic marine sediments: Consequences on the speciation of heavy metals

We investigated the effects of biostimulation and bioagumentation strategies applied to harbor sediments displaying reducing conditions and high concentrations of petroleum hydrocarbons and heavy metals. We compared the microbial efficiency of hydrocarbon removal from sediments maintained for 60 days in anoxic conditions and inoculated with acetate, sulfate-reducing bacterial strains and acetate and sulfate-reducing bacteria. All treatments determined a significant increase in the microbial growth and significant decreases of hydrocarbon contents and of redox potential values. The addition of sulfate-reducing bacterial strains to the sediment was the most efficient treatment for the hydrocarbon removal. In all experiments, significant changes of the heavy metals’ phase repartition were observed. The results reported here suggest that the biodegradation of petroleum hydrocarbons in anoxic marine sediments may be enhanced by stimulating microbial anaerobic metabolism, but care should be applied to monitor the potential changes in the mobility and bioavailability of heavy metals induced by bio-treatments.     

Hydrocarbon concentrations in water and sediments from UK marine waters,determined by fluorescence spectroscopy

Between January 1978 and September 1979 samples of subsurface (1 m) water and surface sediment were collected from sites in the North Sea, English Channel, Irish Sea and a number of estuarine areas. These have been analysed by fluorescence spectroscopy (UVF) in order to provide information on the levels of hydrocarbons generally present in UK marine waters.Total hydrocarbon concentrations (THCs) of water samples ranged from 1.1–74 μg l.^?1 Ekofisk crude oil equivalents, all values greater than 3.5 μg l.^?1 occurring inshore. In offshore areas the mean THCs were: 1.3 μg l.^?1 in the northern North Sea, 1.5 μg l.^?1 in the western Channel, 2.5 μg l.^?1 in the eastern Channel and southern North Sea, and 2.6 μg l.^?1 in the Irish Sea.THCs of sediment samples ranged from 0.27–340 μ g^?1 dry weight Ekofisk crude oil equivalents, the highest concentration being in the Queen's Channel, the main entrance to the River Mersey.     

The effect of bait-digging on the bioavailability of heavy metals from surficial intertidal marine sediments

Extensive bait-digging has been apparent for the last few months at a site on the northeast coast of England known from previous work to be relatively unpolluted by heavy metals. Recent analyses of surface sediment and components of the meiofauna have indicated that there has been a sudden and dramatic rise in the total concentration and bioavailability of metals at this site and evidence is presented that indicates that this is due to the activities of bait-diggers.     

Methylation of lead in marine sediments

Results of incubation experiments with marine sediments containing added amounts of lead in various chemical forms indicated that about 0.03% of lead as Pb(NO₃)₂ underwent methylation. Tetravalent lead, as (CH₃)₃PbOAc, however, was methylated nearly quantitatively in the same time span. Experiments with sediments from four different areas of the British Columbia coastline showed little variation in methylating capacity and no relationship to total ambient lead content. The results suggest that lead contained in mine tailings in particular is not mobilized in detectable amounts by this route.     

Trace metals in Solway Firth sediments

Although the hinterland of the Solway Firth contains deposits of a variety of non-ferrous metals, and coal and steel industries grew there during the industrial revolution, the trace metal content of sediments in the firth is low, and the Solway is the last major unpolluted estuary in Britain.     

Trace metals in sediments of Raritan bay

Marine sediments are the ultimate recipient of nearly all trace metals introduced by man into aquatic ecosystems. This study examined the amounts and distribution of six trace metals (Cd, Cr, Cu, Ni, Pb, Zn) in sediments of Raritan Bay, apolluted estuary. The highest levels of these metals found in Raritan Bay were: Cd-15, Cr-260, Cu-1230, Ni-50, Pb-985, Zn-815. Three metals regimes within Raritan Bay are readily apparent. An area of high values extends across the Bay from the mouth of the Raritan Riverand Arthur Killinto Sandy Hook Bay. This is bounded on the south and northeast by areas of somewhat lower concentrations. An area of relatively low concentrations, near background values, occupies the region at the mouth of the Bay between Sandy Hook peninsula and Coney Island, New York. Metals values from Raritan Bay are compared with other areas and with a few exceptions, the Raritan Bay maximum levels were similar in magnitude to those of areas in Corpus Christi Harbour (U.S.A), Severn Estuary (U.K.), Deep Sea and Florida Lakes, River Blyth (U.K.), dump sites off New York City, various basins off South California, and in Long Island Sound.     

Distribution of heavy metals in marine bivalves, fish and coastal sediments in the Gulf and Gulf of Oman

An assessment of marine contamination due to heavy metals was made in the Gulf and Gulf of Oman based on marine biota (fish and various bivalves) and coastal sediment collected in Bahrain, Oman, Qatar, and the United Arab Emirates (UAE) during 2000-2001. Sediment metal loadings were generally not remarkable, although hot spots were noted in Bahrain (Cu, Hg, Pb, Zn) and on the east coast of the UAE (As, Co, Cr, Ni). Concentrations of As and Hg were typically low in sediments and the total Hg levels in top predator fish commonly consumed in the region were < 0.5 microg g(-1) and posed no threat to public health. Very high Cd concentrations (up to 195 microg g(-1)) in the liver of some fish from southern Oman may result from food-chain bioaccumulation of elevated Cd levels brought into the productive surface waters by upwelling in the region. Very high As concentrations (up to 156 microg g(-1)) were measured in certain bivalve species from the region. Although not certain, the As is probably derived from natural origins rather than anthropogenic contamination.     

Heavy metals in somerset marine organisms

Several independent studies of heavy metal pollution in the Severn Estuary and Bristol Channel are in progress. The County Health Department and Public Analyst have been examining the accumulation of metals in marine shore animals and the food chain, and report their results and conclusions.     

AVO investigations of shallow marine sediments

Amplitude‐variation‐with‐offset (AVO) analysis is based on the Zoeppritz equations, which enable the computation of reflection and transmission coefficients as a function of offset or angle of incidence. High‐frequency (up to 700 Hz) AVO studies, presented here, have been used to determine the physical properties of sediments in a shallow marine environment (20 m water depth). The properties that can be constrained are P‐ and S‐wave velocities, bulk density and acoustic attenuation. The use of higher frequencies requires special analysis including careful geometry and source and receiver directivity corrections. In the past, marine sediments have been modelled as elastic materials. However, viscoelastic models which include absorption are more realistic. At angles of incidence greater than 40°, AVO functions derived from viscoelastic models differ from those with purely elastic properties in the absence of a critical angle of incidence. The influence of S‐wave velocity on the reflection coefficient is small (especially for low S‐wave velocities encountered at the sea‐floor). Thus, it is difficult to extract the S‐wave parameter from AVO trends. On the other hand, P‐wave velocity and density show a considerably stronger effect. Attenuation (described by the quality factor Q) influences the reflection coefficient but could not be determined uniquely from the AVO functions. In order to measure the reflection coefficient in a seismogram, the amplitudes of the direct wave and the sea‐floor reflection in a common‐midpoint (CMP) gather are determined and corrected for spherical divergence as well as source and streamer directivity. At CMP locations showing the different AVO characteristics of a mud and a boulder clay, the sediment physical properties are determined by using a sequential‐quadratic‐programming (SQP) inversion technique. The inverted sediment physical properties for the mud are: P‐wave velocity α=1450±25 m/s, S‐wave velocity β=90±35 m/s, density ρ=1220±45 kg/m³, quality factor for P‐wave Q_P=15±200, quality factor for S‐wave Q_S=10±30. The inverted sediment physical properties for the boulder clay are: α=1620±45 m/s,β=360±200 m/s,ρ=1380±85 kg/m³,Q_P=790±660,Q_S=25±10.     

Trace metals in sediments of New York Bight

Concentrations of chromium, copper, lead, nickel and zinc in superficial sediments in New York Bight are ten to a hundred times greater near waste disposal areas than in uncontaminated sediments. Some wastes are transported by currents north-east towards Long Island and south-east along the Hudson Submarine Valley.     

Spatial distribution of heavy metals in Hong Kong's marine sediments and their human impacts: a GIS-based chemometric approach

A geographic information system (GIS)-based chemometric approach was applied to investigate the spatial distribution patterns of heavy metals in marine sediments and to identify spatial human impacts on global and local scales. Twelve metals (Zn, V, Ni, Mn, Pb, Cu, Cd, Ba, Hg, Fe, Cr and Al) were surveyed twice annually at 59 sites in Hong Kong from 1998 to 2004. Cluster analysis classified the entire coastal area into three areas on a global scale, representing different pollution levels. Backward discriminant analysis, with 84.5% correct assignments, identified Zn, Pb, Cu, Cd, V, and Fe as significant variables affecting spatial variation on a local scale. Enrichment factors indicated that Cu, Cr, and Zn were derived from human impacts while Al, Ba, Mn, V and Fe originated from rock weathering. Principal component analysis further subdivided human impacts and their affected areas in each area, explaining 87%, 84% and 87% of the total variances, respectively. The primary anthropogenic sources in the three areas were (i) anti-fouling paint and domestic sewage; (ii) surface runoff, wastewater, vehicle emissions and marine transportation; and (iii) ship repainting, dental clinics, electronic/chemical industries and leaded fuel, respectively. Moreover, GIS-based spatial analysis facilitated chemometric methods.     

Baseline survey of sediments and marine organisms in Liaohe Estuary: Heavy metals,polychlorinated biphenyls and organochlorine pesticides

A geographically extensive investigation was carried out to analyze the concentrations of heavy metals, PCBs and OCPs in the sediments and marine organisms collected from the Liaohe Estuary. In order to determine the spatial distribution and potential ecological risk of heavy metals, the surface sediments were collected from 44 sites in the Liaohe Estuary. The results showed that the heavy metal contents in the sediments were observed in the following order: Cr (11.2–84.8 mg/kg) > Cu (1.7–47.9 mg/kg) > Pb (4.3–28.3 mg/kg) > As (1.61–12.77 mg/kg) > Cd (0.06–0.47 mg/kg) > Hg (0.005–0.113 mg/kg). In comparison with the concentrations of heavy metals and POPs in other regions, the concentrations of As, Pb and DDTs in the Liaohe Estuary were generally low, and other pollutant concentrations were inconsistent with those reported in other regions. The contamination factor (CF), the pollution load index (PLI), the geoaccumulation index and the potential ecological risk index were used to analyze the pollution situation, which showed that the heavy metal pollution in Liaohe Estuary is mainly dominated by Cd and Hg. The concentrations of the four heavy metals varied significantly in the three kinds of tested organisms (fish, mollusk and crustacean), indicating the different accumulative abilities of the species. The results obtained in this study provide useful information background information for further ecology investigation and management in this region.     

Coprostanols in Antarctic marine sediments: A biomarker for marine mammals and not human pollution

The first analysis of sterols in Antarctic marine sediment cores (Bransfield Strait and McMurdo Sound) is reported here. The isolated sterols in the sediments from Bransfield Strait are comprised mainly of dinosterol (4,23,24-trimethyl-5cholest-22-en-3β-ol), coprostanol (5β-cholestan-3β-ol) and epicoprostanol (5β-cholestan-3-ol) and trace amounts of cholesterol (cholest-5-en-3β-ol). The sediment cores of McMurdo Sound also contain small quantities of coprostanols in addition to large amounts of marine sterols. Dinosterol is a known dinoflagellate chemical marker, whereas coprostanols are currently being used as tracers for sewage contamination. However, sterol composition in Antarctic sediments is expected to be atypical of sewage input and probably different from those of temperate and tropical zones. The coprostanols must therefore arise from the feces of marine mammals, most probably whales which use the region for feeding and spawning. Based on the results of this study, caution should be exercised in the use of coprostanol to estimate the amount of sewage-derived organic matter transported away from impacted coastal areas.     

Application of Avaatech X-ray fluorescence core-scanning in Sr/Ca analysis of speleothems

Application of X-ray fluorescence core-scanning(XRF-CS) on both marine and lake sediments has achieved remarkable results. However, its application has not been widely extended to the research on speleothems. In this study, we measure the Sr abundance and the Sr/Ca ratios of three stalagmites(two aragonite stalagmites, one calcite stalagmite) using the state-of-the-art fourth-generation Avaatech high-resolution XRF core scanner. Through comparisons among different scan paths and among different scan resolutions, as well as comparisons with inductively coupled plasma optical emission spectrometer(ICP-OES), Itrax XRF, and Artax XRF results, we confirm that the Avaatech XRF core scanner could precisely, quickly, and nondestructively analyze the high-resolution Sr abundance of speleothems. Furthermore, we combine the stalagmite δ~(18)O records to explore the paleoclimatic significance of the measured stalagmite Sr/Ca.     

Preservation of reactive organic matter in marine sediments

It is generally assumed that the reactivity of organic matter and the amount preserved in sedimentary deposits necessarily increases with total sedimentation rate. In some environments, such as deltas, where supply of unreactive terrigenous debris may vary independently of reactive organic matter input, the amount of reactive organic material preserved can in fact theoretically correlate either directly or inversely with sedimentation rate. The amount preserved can be shown quantitatively by transport-reaction models to depend on (1) the relative importance of electron acceptor concentration in the overlying water, (2) advection during sedimentation, (3) dilution by sedimentation, (4) solute diffusion, (5) initial flux of organic matter, and (6) the magnitudes of reaction rate constants. Both single reaction rate constant and multiple reaction rate constant models suggest that, at steady state, maximum preservation with respect to a given oxidant occurs when D_sk = w², where D_s = whole sediment diffusion coefficient of the electron acceptor, k = first-order rate constant of the dominant organic fraction, and w = sedimentation rate. This is the likely basis for the reported correlation between average reactivity, k, of carbon in a deposit, percent carbon preservation, and w^1.5–w². Because of the variety of factors which determine these relationships, such correlations are probably valid only within specific classes of depositional environments.     

TBT contamination identified in Antarctic marine sediments

We report for the first time butyltin contamination of near-shore sediments at six sites in the Ross Sea, Antarctica. A very high concentration of 2290 microg Sn kg(-1) sediment was recorded in one sample. The most likely source is abrasion of antifouling paint from the hulls of ice-breakers, but this pattern of contamination is also possible following ship groundings. Antifoulant biocides, such as TBT, have not been considered or detected in Antarctica previously and represent a new challenge to environmental managers and custodians.     

Toxicity studies of elemental sulfur in marine sediments

Elemental sulfur(ES) is a component essential for proper development of animals, but it can be toxic for aquatic organisms. The objectives of the study reported here included determination of ES concentrations in sediment collected in the area of the Gulf of Gdansk(Baltic Sea) and search for the possible correlations with the ecotoxicity results. Sediment samples were collected from four locations: the Vistula River mouth, in the Port Basin, in the area of discharge of the treated wastewater from the Wastewater Treatment Plant(WWTP) and in the area of the sunken World War Ⅱ s/s 'Stuttgart' shipwreck. The levels of elemental sulfur were determined using a gas chromatograph coupled with a mass spectrometer(GC-MS). Toxicity of marine sediment samples was estimated for three biotest organisms-bioluminescent bacteria Vibrio fischeri, crustacean Heterocypris incongruens, and Synapis alba plant. The highest toxicity of sediments for all indicator organisms was observed in samples taken at the place of the shipwreck(2-100%). The same samples had a high sulfur content(16.7-143.2 μg/g dry weight(d.w.))therefore, it was decided to investigate whether the presence of ES in the sediment in the studied area can have an impact on the results of the ecotoxicity determination in real samples. However, the removal of sulfur from the samples resulted in no significant changes in the level of toxicity of the samples. In this research it could not be confirmed that the presence of elemental sulfur is the only factor responsible for the observed sediment toxicity. It seems that other compounds or their mixtures present in the sediment may have a significant influence on the results obtained.