Tim F. Rozan

Chemical speciation drives hydrothermal vent ecology.

The physiology and biochemistry of many taxa inhabiting deep-sea hydrothermal vents have been elucidated; however, the physicochemical factors controlling the distribution of these organisms at a given vent site remain an enigma after 20 years of research. The chemical speciation of particular elements has been suggested as key to controlling biological community structure in these extreme aquatic environments. Implementation of electrochemical technology has allowed us to make in situ measurements of chemical speciation at vents located at the East Pacific Rise (9° 50′ N) and on a scale relevant to the biology. Here we report that significant differences in oxygen, iron and sulphur speciation strongly correlate with the distribution of specific taxa in different microhabitats. In higher temperature (> 30 °C) microhabitats, the appreciable formation of soluble iron-sulphide molecular clusters markedly reduces the availability of free H2S/HS- to vent (micro)organisms, thus controlling the available habitat.

Evidence for iron, copper and zinc complexation as multinuclear sulphide clusters in oxic rivers

The availability and toxicity of trace metals in fresh water are known to be regulated by the complexation of free metal ions with dissolved organic matter. The potential role of inorganic sulphides in binding trace metals has been largely ignored because of the reduced persistence of sulphides in these oxic waters. However, nanomolar concentrations of copper and zinc sulphides have been observed in four rivers in Connecticut and Maryland. Here we report dissolved (< 0.2 µm particle diameter) sulphide concentrations ranging up to 600 nM, with more than 90% being complexed by copper, iron and zinc. These complexes account for up to 20% of the total dissolved Fe and Zn and 45% of the total dissolved Cu. Fourier transform mass spectrometry reveals that these complexes are not simple M(HS)+ protonated species but are higher-order unprotonated clusters (M3S3, M4S 6, M2S4), similar to those found in laboratory solutions and bio-inorganic molecules. These extended structures have high stability constants and are resistant to oxidation and dissociation, which may help control the toxicity of these and other less abundant, but more toxic, trace metals, such as silver, cadmium and mercury.

The influence of size distribution on the particle concentration effect and trace metal partitioning in rivers

The particle concentration effect (p.c.e.) is an unexpected decline in partition coefficients (Kd) as suspended particulate matter (SPM) increases. This anomaly has been attributed to a variety of causes, but most often to the existence of colloidal forms of the adsorbate, which are included, in error, in the dissolved fraction when calculating Kd. To test this hypothesis we have directly measured colloidal, macroparticulate, and truly dissolved metals (Cd, Cu, Pb, Zn, Fe, Al, Mn, Ag) monthly for one year (6/96–7/97) in four Connecticut rivers having a range of ancillary biogeochemical characteristics. These include factors that are all likely to influence partitioning between dissolved and solid phases, such as DOC, pH, and competing cations. The p.c.e. is clearly evident in these rivers, and explicit consideration of colloidal metals eliminates or reduces this anomaly in nearly all cases. Furthermore, a substantial portion of metals occurs in the colloidal fraction, and the amount of colloidal metals increases with SPM. Both of these conditions are necessary for the colloidal model to explain the p.c.e.. Important differences are observed among rivers and metals, and in some cases systematic decreases in Kd continue even when colloidal metals are taken into account. This additional decrease can be eliminated by excluding large particles having negligible surface complexation sites. When corrections are applied for both colloids and large particles, Kd values become truly constant.

210Pb and 137Cs dating methods in lakes: A retrospective study

Abstract210Pb has been used for more than two decades to provide the geochronology of annually deposited sediments and to construct pollution histories. Evidence from some lakes suggests that this radionuclide may be adequately mobile to compromise dating reliability. This study provides one test of that possibility by comparing recent measurements of 210Pb and trace metals to ones carried out more than 20 yrs in the past. 137Cs dating is used to confirm sediment accumulation rates in the recent cores. In the three Connecticut, USA, lakes studied, sediment accumulation rates changed abruptly to higher values between 40-50 yrs ago (increasing by factors of 2.2, 2.9, and 3.0). In all three lakes, rates calculated from 210Pb distributions both above and below this horizon agreed, within measurement uncertainty, in recent and older cores. Furthermore, when the older data were corrected for 20 yrs of burial, the changes in slope in 210Pb distributions occurred at the same depth in each pair of cores. The depth of sharp peaks in concentrations of trace metals also matched. In general, this evidence supports the idea that sediments in these lakes have simply been buried, without significant diagenetic remobilization of 210Pb and trace metals . Nevertheless, some important differences were also observed. For two of the three lakes, there was a significant difference in average sediment accumulation rate during the past 33 yrs as calculated from 137Cs and 210Pb in the recent cores. Most potential causes for this difference can be ruled out, and it appears that one of the two nuclides is remobilized compared to the other. There were also significant differences in the total inventories of both 210Pb and trace metals (both up to 2 ×) between recent and older cores in some cases. This may be due to dissimilar sediment focusing, since it is not known for certain whether the new cores were collected at exactly the same sites as in the past.

The Influence of Sulfides on Soluble Organic-Fe(III) in Anoxic Sediment Porewaters

Solid and colloidal iron oxides are commonly involved in early diagenesis. More readily available soluble Fe(III) should accelerate the cycling of iron (Fe) and sulfur (S) in sediments. Experiments with synthetic solutions (Taillefert et al. 2000) showed that soluble Fe(III) (i.e., <50 nm diameter) reacts at a mercury voltammetric electrode at circumneutral pH if it is complexed by an organic ligand. The reactivity of soluble organic-Fe(III) with sulfide is greatly increased compared to its solid equivalent (e.g., amorphous hydrous iron oxides or goethite). We report here data from two different creeks of the Hackensack Meadowlands District (New Jersey) collected with solid state Au/Hg voltammetric microelectrodes and other conventional techniques, which confirm the existence of soluble organic-Fe(III) in sediments and its interaction with sulfide. Chemical profiles in these two anoxic sediments show the interaction between iron and sulfur during early diagenesis. Soluble organic-Fe(III) and Fe(II) are dominant in a creek where sulfide is negligible. This dominance suggests that the reductive dissolution of iron oxides goes through the dissolution of solid Fe(III), then reduction to Fe(II), or that soluble organic-Fe(III) is formed by chemical or microbial oxidation of organic-Fe(II) complexes. In a creek sediment where sulfide occurs in significant concentration, the reductive dissolution of Fe(III) is followed by formation of FeS(aq), which further precipitates. Dissolved sulfide may influence the fate of soluble organic-Fe(III), but the pH may be the key variable behind this process. The high reactivity of soluble organic-Fe(III) and its mobility may result in the shifting of local reactions, at depths where other electron acceptors are used. These data also suggest that estuarine and coastal sediments may not always be at steady state.

Geochemical factors controlling free Cu ion concentrations in river water

Copper speciation was determined monthly at seven sites on four rivers in southern New England to understand which geochemical factors control free metal ion concentrations in river water. Samples were conventionally filtered (<0.45 μm) and then ultrafiltered (3.000 molecular weight cut-off) to determine Cu speciation in the truly dissolved size fraction. Differential pulse anodic stripping voltammetry (DPASV) was used to quantify natural organic complexation and cathodic stripping square wave voltammetry (CSSWV) to measure directly both Cu sulfide complexes and total EDTA concentrations. The results showed both dissolved organic matter (DOM) and sulfide complexation dominate Cu speciation and control the concentrations of free ion. Free Cu2+ was calculated to be in the subnanomolar range for the majority of the year. Only in the winter months, when concentrations of DOM and metal sulfides complexes were at a minimum were free metal ions directly measurable by DPASV at low nanomolar concentrations. The extent of sulfide complexation appears to be dominated by the size of headwater marshes (upstream sampling sites) and by the amount of sewage treatment plant effluent (downstream sites). DOM complexation was related to the organic matter composition and followed model organic ligands. Indirect evidence suggests variations in river water pH and Ca2+ (metal competition) has only a minor role in Cu complexation. Measured concentrations of total EDTA suggest this synthetic ligand can control Cu speciation in some highly developed watersheds; however, competition from Ni (and possibly Fe) limits the extent of this complexation.

Trace Metals and Radionuclides Reveal Sediment Sources and Accumulation Rates in Jordan Cove, Connecticut

Many small estuaries are influenced by flow restrictions resulting from transportation rights-of-way and other causes. The biogeochemical functioning and history of such systems can be evaluated through study of their sediments. Ten long and six short cores were collected from the length of Jordan Cove, Connecticut, a Long Island Sound subestuary, and analyzed for stratigraphy, radionuclides (14C, 210Pb, 226Ra, 137Cs, and 60Co), and metals (Ag, Cd, Cu, Pb, Zn, Fe, and Al). For at least 3,800 yr, rising sea level has gradually inundated Jordan Cove, filling it with mud similar to that currently being deposited there. Long-term sediment accumulation in the cove averaged close to 0.1 cm yr−1 over the last three millennia. Recent sediment accumulation rates decrease inland from 0.84 cm yr−1 to 0.40 cm yr−1, and are slightly faster than relative sea-level rise at this site (0.3 cm yr−1). Similarity of depth distributions of trace metals was used to confirm relative sediment accumulation rates. 60Co and Ag are derived from sources outside the cove and its watershed, presumably the Millstone nuclear power plant and regional contaminated sediments, respectively. The combined data suggest that Long Island Sound is an important source of sediment to the cove; a minor part of total sediment is supplied from the local watershed. Trace metal levels are strongly correlated with Fe but not with either organic matter or Al. Sediment quality has declined in the cove over the past 60 yr, but only slightly. Cu, Pb, and Zn data correlate strongly with Fe but not with either organic matter or aluminum. Ratios of Ag to Fe and to trace metals suggest that Ag in the cove is derived almost entirely from Long Island Sound. This result supports the notion that Fenormalized Ag can serve as a better tracer of some kinds of contamination than more common and abundant metals, like Cu, Pb, and Zn. *** DIRECT SUPPORT *** A01BY085 00008

Effects of discharge on silver loading and transport in the Quinnipiac River, Connecticut

Silver concentrations were measured in water and sediment samples collected from the Quinnipiac River in Connecticut. This river was chosen for study because of its history of industrialization and high levels of Ag contamination. Sewage treatment plant (STP) effluent accounts for approximately 15% of the total river discharge and approximately 60% of the dissolved Ag in the water column during baseflow conditions. Erosion of contaminated riverbank sediment is the primary source of particulate Ag in the river. Both dissolved and particulate Ag fractions vary as a function of river discharge. Increased discharge due to rain events decreases the relative importance of STP effluent, and thus dilutes the dissolved Ag concentration in the water column. Conversely, increasing discharge results in higher particulate Ag concentrations from increased erosion. The results of this study clearly indicate that both point and non-point sources contribute significantly to Ag loading in this river system, with the level of river discharge determining the relative importance of each.

An anion chromatography/ultraviolet detection method to determine nitrite, nitrate, and sulfide concentrations in saline (pore) waters

Abstract An anion chromatography with ultraviolet detection (IC/UV) method was developed to simultaneously measure NO 3 − , NO 2 − , and HS − concentrations in saline (pore)waters. This method achieves nanomolar detection limits without the need for a Cd/Cu reducing column and requires