James G. Quinn

Enrichment of Heavy Metals and Organic Compounds in the Surface Microlayer of Narragansett Bay, Rhode Island

Concentrations of lead, iron, nickel, copper, fatty acids, hydrocarbons, and chlorinated hydrocarbons are enriched from 1.5 to 50 times in the top 100 to 150 micrometers of Narragansett Bay water relative to the bulk water 20 centimeters below the surface. Trace metal enrichment was observed in the particulate and organic fractions but not in the inorganic fraction. If these substances are concentrated in films only a few molecular layers thick on the water surface, the actual enrichment factor in the films may be well over 104, resulting in extremely high localized pollutant concentrations in the surface microlayer.

Petroleum hydrocarbons in Narragansett Bay: I. Survey of hydrocarbons in sediments and clams (Mercenaria mercenaria)

Abstract Analyses of hydrocarbons in surface sediments from eight stations and in clams (M. mercenaria) from three stations in Narrangansett Bay show that both contain a very complex mixture of hydrocarbons which is not present in clams from Charlestown Pond, a relatively unpolluted coastal pond. This complex mixture of hydrocarbons is present in crude oils and fuel oils, and it is not a likely product of recent biosynthesis by marine organisms. This suggests that the sediments and clams from the areas sampled in Narrangansett Bay are contaminated by petroleum hydrocarbons. Sewage effluents and small oil spills are the most probable sources of the petroleum hydrocarbons.

Uptake and depuration of organic contaminants by blue mussels (Mytilus edulis) exposed to environmentally contaminated sediment

Experiments were designed to expose blue mussels (Mytilus edulis) to contaminated sediment collected from Narragansett Bay, Rhode Island, USA in 1982. Measurements were taken to allow comparisons of the uptake and depuration of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). In addition, concentration factors in the mussels were calculated separately against the dissolved and particulate phase concentrations and the results from the exposure and control systems were compared. Both PAHs and PCBs were rapidly accumulated by the mussels exposed to the contaminated sediment. After the mussels were transferred to control seawater, individual PAHs were depurated with half-lives ranging from 12 to 30 d. Individual PCBs showed depuration half-lives which ranged from 16 to 46 d. Concentration factors in the mussels calculated against the particulate phase concentrations were very different in the exposure and control systems. Concentration factors calculated using only the dissolved phase concentrations (bioconcentration factors) showed excellent agreement in the two systems, possibly an indication that the dissolved phase was the direct source of the contaminants accumulated by the mussels. The bioconcentration factors for PCBs were higher than those of PAHs when compounds with similar n-octanol/water partition coefficients were compared.

Isolation of dissolved organic matter and copper-organic complexes from estuarine waters using reverse-phase liquid chromatography

Abstract Reverse-phase liquid chromatography was used for the isolation of dissolved organic matter and dissolved copper-organic complexes from the estuarine waters of Narragansett Bay, Rhode Island. The procedure isolates 10–30% of the organic matter and up to 50% of the total dissolved copper from various bay samples. Chromatograms obtained by high-performance liquid chromatography of the isolated organic matter showed qualitative differences between sampling stations progressing from the Providence River in the upper bay to the lower bay.

An effect of dissolved nutrient concentrations on alkenone-based temperature estimates

The ratio of 37-carbon diunsaturated to diunsaturated and triunsaturated alkenones (UK′37) produced by some haptophytes is widely used as a proxy for past sea surface temperatures. However, our isothermal culturing experiments with Emiliania huxleyi clone CCMP372 show UK′37 values to also vary with nutrient availability and cell division rate. These results provide a reasonable explanation for large isothermal variation in UK′37 values of single coccolithophorid strains grown in culture. They also suggest that alkenone-based estimates of past sea surface temperatures may have been influenced by dissolved nutrient concentrations as well as by temperature.

Solubilization of hydrocarbons by the dissolved organic matter in sea water

Water samples from Narragansett Bay and the Providence River, and fulvic acid/ saline water solutions were examined for their ability to solubilize n-alkane (n-C16 and n-C20), isoprenoid (pristane) and aromatic (phenanthrene and anthracene) hydrocarbons and dibutyl phthalate. Removal of the dissolved organic matter (D.O.M.) from the natural samples by activated charcoal and by ultra-violet oxidation resulted in a 50–99 per cent decrease in the amounts of n-alkanes and isoprenoid hydrocarbons solubilized. This decrease was directly related to the amount of D.O.M. removed. The solubilities of the aromatic hydrocarbons were unaffected by the D.O.M. Fulvic acid from a marine sediment, surface active organic material isolated at a chloroform/sea water interface, organic material extracted from a marine sediment by sea water, and organic matter contributed by a municipal sewage effluent, promote n-alkane solubility when added to NaCl solutions and re-enhance solubility when added to organic depleted sea water. The solubility of No. 2 fuel oil increased 2.5 times in the presence of fulvic acid (3.7 mg C/l.) with most of the increase seen in the alkane and isoprenoid components. N-Alkane solubility increases in fulvic acid/saline water solutions with increasing pH and reaches a maximum with respect to ionic strength at I = 0.3. There is evidence to suggest that the mode of solubilization of the hydrocarbons is by incorporation into micelles formed by intermolecular association of the surface active humic-type monomers. The presence of ionic species is a prerequisite for micelle formation.

Chemical studies of copper-organic complexes isolated from estuarine waters using C18 reverse-phase liquid chromatography

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography employing C18 Sep-Pak cartridges (Waters Associates). The cartridges were found to have a constant retention efficiency for processing ⩽ 1-l volumes of seawater. Fractionation of the isolated material, by sequential elution of the Sep-Pak with water: methanol mixtures of increasing organic solvent concentration, yielded a fraction of the organic matter with a specific copper activity six times greater than the overall activity for the isolated DOM. Analysis of this fraction by high performance liquid chromatography suggested that the organic components are of intermediate polarity and have appreciable aromatic character. An investigation of the protonation characteristics of the isolated complexes indicated that most of the copper is associated with a broad range of acidic sites on the DOM. Analysis by electron paramagnetic resonance spectroscopy confirmed the organic association of the isolated copper and also suggested the presence of several types of binding sites which probably involve oxygen donor ligands. Studies of the exchange of 64Cu with these binding sites on the isolated DOM indicated that 70% of the sites undergo rapid exchange with copper in seawater while 20% of these sites did not exchange in a 24-h time period.

Stormwater runoff from highways

During four rain events, stormwater runoff samples from Interstate Highway 95 in Rhode Island were collected and analyzed for petroleum hydrocarbons, 14 polycyclic aromatic hydrocarbons (PAHs) and a variety of trace metals. The concentrations were variable throughout the storm events and some of the components responded similarly and others differently depending on the source and form of the component in the runoff. Loading factors as a function of area and traffic volume were developed from the concentration and flow data. Application of the highway runoff loading factors to the Pawtuxet River adjacent to this interstate highway suggests that highway runoff could be the source of over 50% of the annual pollutant loads of solids, PAHs, Pb, and Zn entering this river. It is recommended that highways as a source of non-point pollution to receiving waterbodies should be included as a part of any river and estuarine water quality management planning exercise.

Early diagenesis of fatty acids and isoprenoid alcohols in estuarine and coastal sediments

Fatty acids and isoprenoid alcohols were analyzed in river, estuarine, and coastal sediment cores: (1) to investigate the distribution of these lipids among the unbound phase. those bound or closely associated with humic substances, and those bound or closely associated with the huminkerogen and clay mineral matrix. (2) to investigate the diagenetic changes of these lipids with depth in the sediments. and (3) to obtain information on the use of these compounds as organic tracers in marine sediments. Results confirm earlier observations that fatty acids are rapidly altered in marine sediments Both the total and the individual fatty acids decrease in concentration with depth in the sediments: unsaturated acids decrease faster than saturated acids and unbound acids decrease faster than bound acids Approximately 8–62% of the fatty acids were unbound. 2–22% were associated with humic substances. and 38–86% were associated with the residual organic-mineral matrix. Qualitative differences also exist between the fatty acids associated with the unbound, humic, and residual fractions. The ratio of trans/cis geometric isomers of the fatty acids generally increases downcore. with no rearrangement of the double bond positions within the molecules. Either the cis isomer is being preferentially degraded with depth in the sediments, or there is a low temperature, clay catalyzed conversion of the cis isomers to the trans isomers occurring down the cores. Phytol was the major alcohol present in the sediments and does not appear to be altered as rapidly as the fatty acids. Less than 10% of the total phytol (PHY) plus dihydrophytol (DHP) was present as DHP and no trend could be discerned between PHY and DHP with depth or with unbound, humic, and residual material in the cores. All of the isolated DHP appeared to be present as the RRR stereoisomer. Along with the absence of phytane in the cores, this observation suggests that the reduction of phytol to dihydrophytol is microbially mediated in the upper layer of the sediment.

Sources of petroleum hydrocarbons in urban runoff

In an effort to provide a better understanding of the sources of petroleum hydrocarbons in urban runoff, petroleum products as well as probable source materials were analyzed for hydrocarbons and trace metals and then compared to urban runoff samples from four different land use areas. The petroleum products considered were No. 2 and No. 6 fuel oils, used and virgin crankcase oils, and gasoline. Source materials included street dust, roadside soil, roadside vegetation, and atmospheric fallout; and the land use categories were commercial, residential, interstate highway, and industrial areas. The samples were compared on the basis of hydrocarbon (saturated and aromatic) and trace metal (Cd, Pb, Mn, Cu, Fe, Zn) loadings and distributions. Results indicated that the hydrocarbon content in runoff at all four land use sites originated primarily from used crankcase oil, with a small amount of No. 2 fuel oil detected at the industrial site. Only a small portion of the crankcase oil component came from the sources surveyed, and the majority of this oil probably came from: (1) oil drops within the driving lanes on the road surfaces or deposits in parking areas, and/or (2) direct dumping of waste crankcase oil down storm drains.