Robert P. Trocine

A Decline in Lead Transport by the Mississippi River

Inputs of pollutant lead to the Gulf of Mexico from the Mississippi River have declined by about 40 percent within the past decade. This decrease has been determined from annual lead loads of the Mississippi River and from the lead record in Mississippi Delta sediments. The observed trend is consistent with reduced consumption of lead in gasoline in the United States. More than 90 percent of the riverborne lead is associated with suspended sediments. Most of this particle-bound lead is deposited within 50 kilometers of the river mouth and is not easily leached at pH values above 3.

Distribution and chemistry of suspended particles from an active hydrothermal vent site on the Mid-Atlantic Ridge at 26°N

Suspended particles were collected from an area of active hydrothermal venting at the Trans-Atlantic Geotraverse (TAG) Hydrothermal Field on the Mid-Atlantic Ridge and analyzed for Fe, Mn, Cd, Zn, Cu, V, Ni, Cr, Pb, Mg, Ca, Al and Si. Rapid advection of vent-derived precipitates produced a lens with total suspended matter (TSM) loadings of 14–60 μg/l at 200–700 m above the seafloor; TSM concentrations > 60 μg/l were observed only at near-vent sites. The distribution of suspended particles correlated well with increased dissolved Mn concentrations and particulate Fe values near the vent source. Particulate Fe values decreased linearly relative to TSM concentrations as hydrothermal precipitates mixed with background suspended matter. Near-vent precipitates were characterized by up to 35% Fe, 2% Zn, 0.6% Cu and > 100 μg/g Cd. In comparison to Fe, particulate Cd, Zn and Cu values decreased dramatically away from the vent source. This trend supports differential settling and/or dissolution of Cd-, Zn- and Cu-bearing phases. Particulate Mn and Fe values were inversely related with only 50 μg Mn/g in the near-vent particles. At near-vent sites, > 99% of the total Mn was in solution; this fraction decreased to 75–80% at background TSM values. In contrast to Cd, Zn and Cu, particulate V levels show a continuous, linear decrease with particulate Fe values. This trend is explained by adsorption of V on Fe-oxides in the vent plume. Scavenging of Cr, Pb and Mg by hydrothermal precipitates is also suggested by the data. Nickel and Al values were low in near-vent particles at < 100 and < 3 μg/g, respectively. The complementary behavior of dissolved Mn and particulate trace metals provides a useful framework for studying broad aspects of hydrothermal plume processes.

Transport of particulate organic carbon by the Mississippi River and its fate in the Gulf of Mexico

This study was designed to determine the amount of particulate organic carbon (POC) introduced to the Gulf of Mexico by the Mississippi River and assess the influence of POC inputs on the development of hypoxia and burial of organic carbon on the Louisiana continental shelf. Samples of suspended sediment and supporting hydrographic data were collected from the river and >50 sites on the adjacent shelf. Suspended particles collected in the river averaged 1.8±0.3% organic carbon. Because of this uniformity, POC values (in μmol l−1) correlated well with concentrations of total suspended matter. Net transport of total organic carbon by the Mississippi-Atchafalaya River system averaged 0.48×1012 moles y−1 with 66% of the total organic carbon carried as POC. Concentrations of POC decreased from as high as 600 μmol l−1 in the river to <0.8 μmol l−1 in offshore waters. In contrast, the organic carbon fraction of the suspended matter increased from <2% of the total mass in the river to >35% along the shelf at ≥10 km from the river mouth. River flow was a dominant factor in controlling particle and POC distributions; however, time-series data showed that tides and weather fronts can influence particle movement and POC concentrations. Values for apparent oxygen utilization (AOU) increased from ∼60 μmol l−1 to >200 μmol l−1 along the shelf on approach to the region of chronic hypoxia. Short-term increases in AOU were related to transport of more particle-rich waters. Sediments buried on the shelf contained less organic carbon than incoming river particles. Orgamic carbon and δ13C values for shelf sediments indicated 3 that large amounts of both terrigenous and marine organic carbon are being decomposed in shelf waters and sediments to fuel observed hypoxia.

Trace metals in hydrothermal solutions from Cleft segment on the southern Juan de Fuca Ridge

Concentrations of trace metals in Fe- and Cl-rich hydrothermal solutions from the southern Juan de Fuca Ridge (SJFR) have been determined and corrected for residual precipitates formed in the sampler. Precipitate corrections for Ag, Cd, Cu, Mo, Pb, Sb, and Zn were variable, contributing an average of 20% to total solution concentrations whereas corrections for Co averaged less than 5% and essentially no corrections were required for Fe and Mn. Values for Cu, Co, and Mo in these solutions showed a strong dependence on temperature with sharp decreases in concentrations as temperatures decreased to less than 320°C. In addition, and unlike most other metals studied, all vent fluids from the SJFR were almost completely depleted in Mo relative to seawater values of about 110 nmol kg−1. In contrast to the Cu-Co-Mo group, concentrations of Ag, Cd, Sb, and Pb correlated well with those for Zn and are presumed to follow a distribution that is influenced less by temperature over the 246 to 332°C range encountered in this study and more by the combined chemical processes that control Zn levels along the transport pathway from the deep reaction zone to the vent orifice.

Distribution and Chemistry of Manganese, Iron, and Suspended Particulates in Orca Basin

The intense halocline and redoxcline in the Orca Basin, northwest Gulf of Mexico, induce dramatic water column profiles for manganese, iron, and suspended particulates. Within a 17 m interval, the salinity of the basin water increases from 66 to ≈260 & permil and dissolved oxygen decreases to zero. Midway through this transition zone, concentrations of suspended matter peak at ≈900 μg/liter. Dissolved iron and manganese concentrations in the anoxic brine increase from oceanic values to maxima of 1.6 and 22 mg/liter, respectively. Upward migration of dissolved manganese from the brine leads to production of manganese-rich particles in the slightly oxygenated overlying water.

Real-time observation of dispersed hydrothermal plumes using nephelometry: examples from the Mid-Atlantic Ridge

Abstract As part of the 1984–1985 NOAA VENTS program on the Mid-Atlantic Ridge, nephelometry was used to provide real-time detection and tracking of dispersed hydrothermal plumes. At all nine 1984 study sites, hydrothermal activity was detected by in-situ, real-time nephelometer measurements and later confirmed by dissolved Mn and particulate Fe measurements. These same techniques were employed in a site-specific survey of the Trans-Atlantic Geotraverse (TAG) area in 1985 where large water-column anomalies in turbidity and in dissolved Mn helped lead to the discovery of high-temperature black smokers. The optical response of the nephelometer was to hydrothermally-derived particulate matter. Thus strong correlations existed between the nephelometer readings and total suspended matter (r = 0.98, n = 34), and particulate Fe (r = 0.88, n = 32). In addition, digital nephelometer data correlated well with dissolved Mn (r = 0.88; n = 78) throughout a large concentration range (0.2–31.0 nmol/kg). These data provide good evidence for the utility of in-situ nephelometer measurements for locating and surveying plumes from hydrothermal vents. It also appears possible, within limits, to predict concentrations of in-situ total suspended matter, of particulate Fe and of dissolved Mn.

Biogeochemical analysis of ancient Pacific Cod bone suggests Hg bioaccumulation was linked to paleo sea level rise and climate change

Deglaciation at the end of the Pleistocene initiated major changes in ocean circulation and distribution. Within a brief geological time, large areas of land were inundated by sea-level rise and today global sea level is 120 m above its minimum stand during the last glacial maximum. This was the era of modern sea shelf formation; climate change caused coastal plain flooding and created broad continental shelves with innumerable consequences to marine and terrestrial ecosystems and human populations. In Alaska, the Bering Sea nearly doubled in size and stretches of coastline to the south were flooded, with regional variability in the timing and extent of submergence. Here we suggest how past climate change and coastal flooding are linked to mercury bioaccumulation that could have had profound impacts on past human populations and that, under conditions of continued climate warming, may have future impacts. Biogeochemical analysis of total mercury (tHg) and 13C/15N ratios in the bone collagen of archaeologically recovered Pacific Cod (Gadus macrocephalus) bone shows high levels of tHg during early/mid-Holocene. This pattern cannot be linked to anthropogenic activity or to food web trophic changes, but may result from natural phenomena such as increases in productivity, carbon supply and coastal flooding driven by glacial melting and sea-level rise. The coastal flooding could have led to increased methylation of Hg in newly submerged terrestrial land and vegetation. Methylmercury is bioaccumulated through aquatic food webs with attendant consequences for the health of fish and their consumers, including people. This is the first study of tHg levels in a marine species from the Gulf of Alaska to provide a time series spanning nearly the entire Holocene and we propose that past coastal flooding resulting from climate change had the potential to input significant quantities of Hg into marine food webs and subsequently to human consumers.

Chemical and biological assessment of two offshore drilling sites in the Alaskan Arctic.

A retrospective chemical and biological study was carried out in Camden Bay, Alaskan Beaufort Sea, where single exploratory oil wells were drilled at two sites more than two decades ago. Barium from discharged drilling mud was present in sediments at concentrations as high as 14%, ~200 times above background, with significantly higher concentrations of Ba, but not other metals, within 250 m of the drilling site versus reference stations. Elevated concentrations of Cr, Cu, Hg and Pb were found only at two stations within 25 m of one drilling site. Concentrations of total polycyclic aromatic hydrocarbons (TPAH) were not significantly different at reference versus drilling-site stations; however, TPAH were elevated in Ba-rich layers from naturally occurring perylene in ancient formation cuttings. Infaunal biomass and species abundance were not significantly different at reference versus drilling-site stations; infauna were less diverse at drilling-site stations. Our assessment showed that discharges from single wells within large areas caused minimal long-term, adverse impacts to the benthic ecosystem.

A Risk Evaluation of Metals in Crude Oils

All crude oils contain trace quantities of naturally occurring metals, however, few data have been published on the specific metal content of crude oils. In this study, the metals concentrations in 26 crude oils from North America, South America, the North Sea, the Middle East, and Far East Asia were determined. The crude oils represent both a range of geographical production areas and a range of crude oil types, with the oils having API gravity values ranging from 12° to 46°. The concentrations of 18 metals were determined, and the potential human health risks associated with the metals were evaluated, assuming standard exposure scenarios. The potential for ecological impact was also evaluated by comparing the metal concentrations to ecological soil screening level benchmarks. The results indicate that many metals are present at such low levels that there is no need to consider them as chemicals of concern for purposes of site characterizations and risk assessments at sites where accidental and/or historical crude oil releases have occurred.

Assessing the Potential for Enhanced Bio Accumulation of Heavy Metals from Produced Water Discharges to the Gulf of Mexico

More than 140 million m3 of produced water per year are discharged to surface water from more than 3000 production platforms in the northern Gulf of Mexico (Reilly et al., 1991; LeBlanc, 1994). Concentrations of heavy metals in this produced water can be enriched by factors of 10 to greater than 10,000 relative to ambient seawater (Boesch and Rabalais, 1989; Ray and Engelhardt, 1992). Concern for the fate and effects of such discharges continues to prompt a variety of research and monitoring programs.