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G.R. Helz

Publications and source records attributed to G.R. Helz.

3 recordsLinked to original sources

Reconstructing the rise of recent coastal anoxia; molybdenum in Chesapeake Bay sediments

Sporadic, direct observations over a 50 yr period inadequately characterize the history of seasonal hypoxia and anoxia in Chesapeake Bay, alarge estuary threatened by eutrophication. Here, we undertake a reconstruction of 20th century oxygen depletion in this estuary using Mo concentrations in 210Pb-dated sediments; Cu concentrations are used to control for anthropogenic influences. Cores from the central channel display mild Mo enrichments above crustal backgrounds (up to 5 ??g/g) and strong Cu enrichments (up to 35 ??g/g). Temporally, Cu enrichment (mostly anthropogenic) began earlier and stabilized in the last two thirds of the 20th century. In contrast, Mo enrichment has grown during the last two thirds of the century. Molybdenum enrichment is mostly hydrogenic, except in a section of the channel that receives additional Mo from erosion of Early Miocene shore deposits. Two geochemical mechanisms promote Mo enrichment: Manganese refluxing concentrates dissolved MoO24- at the sediment-water interface and sulfide substitution into MoO24- produces thiomolybdates, which can be fixed by particles. The Mo enrichment mechanisms operate primarily during periods when bottom waters are anoxic and thiomolybdate formation can occur near the sediment-water interface. This implies a temporal coupling between water-column anoxia and Mo fixation even though fixation occurs only within sediments. The Mo enrichment profiles suggest that Chesapeake Bay has experienced growing O2 depletion since the first half of the 20th century, but especially after 1960. Copyright ?? 2001 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta

Osmium isotopes demonstrate distal transport of contaminated sediments in Chesapeake Bay

Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post- Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post-Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.

Environmental Science & Technology

Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10-3.6 - 10-4.3. When aHS- approaches the action point, Mo becomes reactive to particles containing transition metals (e.g., Fe). We conjecture that thiols, including humic-bound thiol groups, also switch Mo behavior. In contrast to previous ideas, our model for Mo scavenging deemphasizes the role of reduction from Mo(VI) to Mo(V) as the initial step in scavenging; instead, we emphasize the ease with which Mo forms covalent bonds to transition metals and organic molecules via S bridges.

Geochimica et Cosmochimica Acta