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USGS2006

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (222Rn, 223,224,226,228Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5??mg L- 1) close to zero salinity and increased several-fold (??? 18??mg L- 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet. Surface water-column 222Rn activities were most elevated (> 28??dpm L- 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (223,224,226,228Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess 226Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 ?? 105??m3 d- 1 (20-74??L m- 2 d- 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH4+ and PO4- 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5????mol m- 2 d- 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates. ?? 2006 Elsevier B.V. All rights reserved.

Marine Chemistry↗

USGS2007

Diurnal variation of oxygen and carbonate system parameters in Tampa Bay and Florida Bay

Oxygen and carbonate system parameters were measured, in situ, over diurnal cycles in Tampa Bay and Florida Bay, Florida. All system parameters showed distinct diurnal trends in Tampa Bay with an average range of diurnal variation of 39.1 μmol kg − 1 for total alkalinity, 165.1 μmol kg − 1 for total CO 2 , 0.22 for pH, 0.093 mmol L − 1 for dissolved oxygen, and 218.1 μatm for pCO 2 . Average range of diurnal variation for system parameters in Tampa Bay was 73% to 93% of the seasonal range of variability for dissolved oxygen and pH. All system parameters measured in Florida Bay showed distinct variation over diurnal time-scales. However, clear diurnal trends were less evident. The average range of diurnal variability in Florida Bay was 62.8 μmol kg − 1 for total alkalinity, 130.4 μmol kg − 1 for total CO 2 , 0.13 for pH, 0.053 mmol L − 1 for dissolved oxygen, and 139.8 μatm for pCO 2 . The average range of diurnal variation was 14% to 102% of the seasonal ranges for these parameters. Diurnal variability in system parameters was most influenced by primary productivity and respiration of benthic communities in Tampa Bay, and by precipitation and dissolution of calcium carbonate in Florida Bay. Our data indicate that use of seasonal data sets without careful consideration of diurnal variability may impart significant error in calculations of annual carbon and oxygen budgets. These observations reinforce the need for higher temporal resolution measurements of oxygen and carbon system parameters in coastal ecosystems.

Florida↗

USGS2007

Tampa Bay as a model estuary for examining the impact of human activities on biogeochemical processes: an introduction

Tampa Bay is a shallow, Y-shaped coastal embayment that is located along the center of the Florida Platform – an expansive accumulation of Cretaceous–Tertiary shallow-water carbonates and evaporites that were periodically exposed during glacio–eustatic sea level fluctuations. As a consequence, extensive karstification likely had a controlling impact on the geologic evolution of Tampa Bay. Despite its large aerial size (∼ 1000 km 2 ), Tampa Bay is relatively shallow (mean depth = 4 m) and its watershed (6700 km 2 ) is among the smallest in the Gulf of Mexico. About 85% of all freshwater inflow (mean = 63 m 3 s -1 ) to the bay is carried by four principal tributaries (Orlando et al., 1993). Groundwater makes up an important component of baseflow of these coastal streams and may also be important in delivering nutrients and other constituents to the bay proper by submarine groundwater discharge.

Florida↗

USGS2008

Seasonal changes in submarine groundwater discharge to coastal salt ponds estimated using 226Ra and 228Ra as tracers

Submarine groundwater discharge (SGD) to coastal southern Rhode Island was estimated from measurements of the naturally-occurring radioisotopes 226Ra (t1/2 = 1600??y) and 228Ra (t1/2 = 5.75??y). Surface water and porewater samples were collected quarterly in Winnapaug, Quonochontaug, Ninigret, Green Hill, and Pt. Judith-Potter Ponds, as well as nearly monthly in the surface water of Rhode Island Sound, from January 2002 to August 2003; additional porewater samples were collected in August 2005. Surface water activities ranged from 12-83??dpm 100??L- 1 (60??dpm = 1??Bq) and 21-256??dpm 100??L- 1 for 226Ra and 228Ra, respectively. Porewater 226Ra activities ranged from 16-736??dpm 100??L- 1 (2002-2003) and 95-815??dpm 100??L- 1 (2005), while porewater 228Ra activities ranged from 23-1265??dpm 100??L- 1. Combining these data with a simple box model provided average 226Ra-based submarine groundwater fluxes ranging from 11-159??L m- 2 d- 1 and average 228Ra-derived fluxes of 15-259??L m- 2 d- 1. Seasonal changes in Ra-derived SGD were apparent in all ponds as well as between ponds, with SGD values of 30-472??L m- 2 d- 1 (Winnapaug Pond), 6-20??L m- 2 d- 1 (Quonochontaug Pond), 36-273??L m- 2 d- 1 (Ninigret Pond), 29-76??L m- 2 d- 1 (Green Hill Pond), and 19-83??L m- 2 d- 1 (Pt. Judith-Potter Pond). These Ra-derived fluxes are up to two orders of magnitude higher than results predicted by a numerical model of groundwater flow, estimates of aquifer recharge for the study period, and values published in previous Ra-based SGD studies in Rhode Island. This disparity may result from differences in the type of flow (recirculated seawater versus fresh groundwater) determined using each technique, as well as variability in porewater Ra activity. ?? 2007 Elsevier B.V. All rights reserved.

Marine Chemistry↗

USGS2008

Submarine groundwater discharge and nutrient addition to the coastal zone and coral reefs of leeward Hawai'i

Multiple tracers of groundwater input (salinity, Si, 223Ra, 224Ra, and 226Ra) were used together to determine the magnitude, character (meteoric versus seawater), and nutrient contribution associated with submarine groundwater discharge across the leeward shores of the Hawai'ian Islands Maui, Moloka'i, and Hawai'i. Tracer abundances were elevated in the unconfined coastal aquifer and the nearshore zone, decreasing to low levels offshore, indicative of groundwater discharge (near-fresh, brackish, or saline) at all locations. At several sites, we detected evidence of fresh and saline SGD occurring simultaneously. Conservative estimates of SGD fluxes ranged widely, from 0.02-0.65??m3??m- 2 d- 1at the various sites. Groundwater nutrient fluxes of 0.04-40??mmol N m- 2 d- 1 and 0.01-1.6??mmol P m- 2 d- 1 represent a major source of new nutrients to coastal ecosystems along these coasts. Nutrient additions were typically greatest at locations with a substantial meteoric component in groundwater, but the recirculation of seawater through the aquifer may provide a means of transferring terrestrially-derived nutrients to the coastal zone at several sites. ?? 2007 Elsevier B.V. All rights reserved.

Marine Chemistry↗

USGS2008

Eddy correlation measurements of submarine groundwater discharge

This paper presents a new, non-invasive means of quantifying groundwater discharge into marine waters using an eddy correlation approach. The method takes advantage of the fact that, in virtually all aquatic environments, the dominant mode of vertical transport near the sediment–water interface is turbulent mixing. The technique thus relies on measuring simultaneously the fluctuating vertical velocity using an acoustic Doppler velocimeter and the fluctuating salinity and/or temperature using rapid-response conductivity and/or temperature sensors. The measurements are typically done at a height of 5–15 cm above the sediment surface, at a frequency of 16 to 64 Hz, and for a period of 15 to 60 min. If the groundwater salinity and/or temperature differ from that of the water column, the groundwater specific discharge (cm d− 1) can be quantified from either a heat or salt balance. Groundwater discharge was estimated with this new approach in Salt Pond, a small estuary on Cape Cod (MA, USA). Estimates agreed well with previous estimates of discharge measured using seepage meters and 222Rn as a tracer. The eddy correlation technique has several desirable characteristics: 1) discharge is quantified under in-situ hydrodynamic conditions; 2) salinity and temperature can serve as two semi-independent tracers of discharge; 3) discharge can be quantified at high temporal resolution, and 4) long-term records of discharge may be possible, due to the low power requirements of the instrumentation.

Massachussetts↗

USGS2009

Methane sources in gas hydrate-bearing cold seeps: Evidence from radiocarbon and stable isotopes

Fossil methane from the large and dynamic marine gas hydrate reservoir has the potential to influence oceanic and atmospheric carbon pools. However, natural radiocarbon ( 14 C) measurements of gas hydrate methane have been extremely limited, and their use as a source and process indicator has not yet been systematically established. In this study, gas hydrate-bound and dissolved methane recovered from six geologically and geographically distinct high-gas-flux cold seeps was found to be 98 to 100% fossil based on its 14 C content. Given this prevalence of fossil methane and the small contribution of gas hydrate (??? 1%) to the present-day atmospheric methane flux, non-fossil contributions of gas hydrate methane to the atmosphere are not likely to be quantitatively significant. This conclusion is consistent with contemporary atmospheric methane budget calculations. In combination with ?? 13 C- and ??D-methane measurements, we also determine the extent to which the low, but detectable, amounts of 14 C (~ 1-2% modern carbon, pMC) in methane from two cold seeps might reflect in situ production from near-seafloor sediment organic carbon (SOC). A 14 C mass balance approach using fossil methane and 14 C-enriched SOC suggests that as much as 8 to 29% of hydrate-associated methane carbon may originate from SOC contained within the upper 6??m of sediment. These findings validate the assumption of a predominantly fossil carbon source for marine gas hydrate, but also indicate that structural gas hydrate from at least certain cold seeps contains a component of methane produced during decomposition of non-fossil organic matter in near-surface sediment.

Marine Chemistry↗

USGS2013

Environmental assessment of metal exposure to corals living in Castle Harbour, Bermuda

Environmental contamination in Castle Harbour, Bermuda, has been linked to the dissolution and leaching of contaminants from the adjacent marine landfill. This study expands the evidence for environmental impact of leachate from the landfill by quantitatively demonstrating elevated metal uptake over the last 30 years in corals growing in Castle Harbour. Coral Pb/Ca, Zn/Ca and Mn/Ca ratios and total Hg concentrations are elevated relative to an adjacent control site in John Smith's Bay. The temporal variability in the Castle Harbour coral records suggests that while the landfill has increased in size over the last 35 years, the dominant input of metals is through periodic leaching of contaminants from the municipal landfill and surrounding sediment. Elevated contaminants in the surrounding sediment suggest that resuspension is an important transport medium for transferring heavy metals to corals. Increased winds, particularly during the 1990s, were accompanied by higher coral metal composition at Castle Harbour. Coupled with wind-induced resuspension, interannual changes in sea level within the Harbour can lead to increased bioavailability of sediment-bound metals and subsequent coral metal assimilation. At John Smith's Bay, large scale convective mixing may be driving interannual metal variability in the coral record rather than impacts from land-based activities. Results from this study provide important insights into the coupling of natural variability and anthropogenic input of contaminants to the nearshore environment.

Castle Harbour↗

USGS2014

An intercomparison of three methods for the large-scale isolation of oceanic dissolved organic matter

Dissolved organic matter (DOM) was isolated from large volumes of deep (674 m) and surface (21 m) ocean water via reverse osmosis/electrodialysis (RO/ED) and two solid-phase extraction (SPE) methods (XAD-8/4 and PPL) at the Natural Energy Laboratory of Hawaii Authority (NELHA). By applying the three methods to common water samples, the efficiencies of XAD, PPL and RO/ED DOM isolation were compared. XAD recovered 42% of dissolved organic carbon (DOC) from deep water (25% with XAD-8; 17% with XAD-4) and 30% from surface water (16% with XAD-8; 14% with XAD-4). PPL recovered 61 ± 3% of DOC from deep water and 61% from surface water. RO/ED recovered 82 ± 3% of DOC from deep water, 14 ± 3% of which was recovered in a sodium hydroxide rinse, and 75 ± 5% of DOC from surface water, with 12 ± 2% in the sodium hydroxide rinse. The highest recoveries of all were achieved by the sequential isolation of DOC, first with PPL and then via RO/ED. This combined technique recovered 98% of DOC from a deep water sample and 101% of DOC from a surface water sample. In total, 1.9, 10.3 and 1.6 g-C of DOC were collected via XAD, PPL and RO/ED, respectively. Rates of DOC recovery using the XAD, PPL and RO/ED methods were 10, 33 and 10 mg-C h − 1 , respectively. Based upon C/N ratios, XAD isolates were heavily C-enriched compared with water column DOM, whereas RO/ED and PPL ➔ RO/ED isolate C/N values were most representative of the original DOM. All techniques are suitable for the isolation of large amounts of DOM with purities suitable for most advanced analytical techniques. Coupling PPL and RO/ED techniques may provide substantial progress in the search for a method to quantitatively isolate oceanic DOC, bringing the entirety of the DOM pool within the marine chemist's analytical window.

Marine Chemistry↗

USGS2016

The use of amino acid indices for assessing organic matter quality and microbial abundance in deep-sea Antarctic sediments of IODP Expedition 318

The Adélie Basin, located offshore of the Wilkes Land margin, experiences unusually high sedimentation rates (~ 2 cm yr − 1 ) for the Antarctic coast. This study sought to compare depthwise changes in organic matter (OM) quantity and quality with changes in microbial biomass with depth at this high-deposition site and an offshore continental margin site. Sediments from both sites were collected during the International Ocean Drilling (IODP) Program Expedition 318. Viable microbial biomass was estimated from concentrations of bacterial-derived phospholipid fatty acids, while OM quality was assessed using four different amino acid degradation proxies. Concentrations of total hydrolysable amino acids (THAA) measured from the continental margin suggest an oligotrophic environment, with THAA concentrations representing only 2% of total organic carbon with relative proportions of non-protein amino acids β-alanine and γ-aminobutyric acid as high as 40%. In contrast, THAA concentrations from the near-shore Adélie Basin represent 40%–60% of total organic carbon. Concentrations of β-alanine and γ-aminobutyric acid were often below the detection limit and suggest that the OM of the basin as labile. DI values in surface sediments at the Adélie and margin sites were measured to be + 0.78 and − 0.76, reflecting labile and more recalcitrant OM, respectively. Greater DI values in deeper and more anoxic portions of both cores correlated positively with increased relative concentrations of phenylalanine plus tyrosine and may represent a change of redox conditions, rather than OM quality. This suggests that DI values calculated along chemical profiles should be interpreted with caution. THAA concentrations, the percentage of organic carbon (C AA %) and total nitrogen (N AA %) represented by amino acids at both sites demonstrated a significant positive correlation with bacterial abundance estimates. These data suggest that the selective degradation of amino acids, as indicated by THAA concentrations, C AA % or N AA % values may be a better proxy for describing the general changes in sedimentary bacterial abundances than total organic matter or bulk sedimentation rates.

Marine Chemistry↗

USGS2017

Perspectives on chemical oceanography in the 21st century: Participants of the COME ABOARD Meeting examine aspects of the field in the context of 40 years of DISCO

The questions that chemical oceanographers prioritize over the coming decades, and the methods we use to address these questions, will define our field's contribution to 21st century science. In recognition of this, the U.S. National Science Foundation and National Oceanic and Atmospheric Administration galvanized a community effort (the Chemical Oceanography MEeting: A BOttom-up Approach to Research Directions, or COME ABOARD) to synthesize bottom-up perspectives on selected areas of research in Chemical Oceanography. Representing only a small subset of the community, COME ABOARD participants did not attempt to identify targeted research directions for the field. Instead, we focused on how best to foster diverse research in Chemical Oceanography, placing emphasis on the following themes: strengthening our core chemical skillset; expanding our tools through collaboration with chemists, engineers, and computer scientists; considering new roles for large programs; enhancing interface research through interdisciplinary collaboration; and expanding ocean literacy by engaging with the public. For each theme, COME ABOARD participants reflected on the present state of Chemical Oceanography, where the community hopes to go and why, and actionable pathways to get there. A unifying concept among the discussions was that dissimilar funding structures and metrics of success may be required to accommodate the various levels of readiness and stages of knowledge development found throughout our community. In addition to the science, participants of the concurrent Dissertations Symposium in Chemical Oceanography (DISCO) XXV, a meeting of recent and forthcoming Ph.D. graduates in Chemical Oceanography, provided perspectives on how our field could show leadership in addressing long-standing diversity and early-career challenges that are pervasive throughout science. Here we summarize the COME ABOARD Meeting discussions, providing a synthesis of reflections and perspectives on the field.

Marine Chemistry↗

USGS2018

Reductive dechlorination rates of 4,4′-DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene) in sediments of the Palos Verdes Shelf, CA

Wastes from the world's largest manufacturer of DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene) were released into the Los Angeles County municipal sewer system from 1947 to 1971. Following primary treatment, the effluent was discharged through a submarine outfall system whereupon a portion of the DDT and associated degradation products were deposited in sediments of the Palos Verdes Shelf (PVS). Parent DDT is present only in trace amounts in the sediments today, the vast majority having been transformed to DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene) shortly following deposition. Previously believed to be inert, DDE is slowly being converted to DDMU (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene) and DDMU to DDNU (1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene) via microbially-mediated reductive dechlorination (RDC). Kinetic and compositional data suggest that this process began sometime in the mid- to late 1970s. Rates of DDE RDC in shelf sediments are spatially variable and have proven difficult to determine accurately. This limits our ability to understand the factors controlling RDC rates and to predict the course of natural recovery. In the present study, concentrations of ten DDT compounds and twelve PCB (polychlorinated biphenyl) congeners were determined in cores collected at two locations on the PVS (stations 3C, 6C, ~7km and ~2km downcurrent from the outfalls, respectively). DDE inventories, normalized to those of non-degrading PCB congeners having similar physico-chemical properties, were modeled to yield first-order RDC rates for the period 1981–2010. Average rates at stations 3C and 6C were 0.044±0.004 and 0.008±0.002yr −1 , respectively, with depth-dependent RDC rates at station 3C (1992–2003) ranging from 0.0025 to 0.102yr −1 . Comparison of RDC and total loss (i.e., RDC+physical loss) rates suggests that the average per cent loss of DDE due to RDC is ~90% at station 3C (1981–2010) and ~57% at station 6C (1992–2010). Trajectories of adjusted molar inventories of DDE, DDMU, and DDNU were forecast using a first-order multi-step reaction series (M-SRS) model. The results for DDE are consistent with the normalization procedure; RDC rates at stations 3C and 6C were 0.036±0.002yr −1 and 0.010±0.001yr −1 , respectively. At station 6C, the DDE to DDMU transformation appears to be the rate limiting step in the reaction sequence, DDE k 1 → DDMU k 2 → DDNU k3 → unidentified compound(s), whereas at station 3C RDC rates for DDE and DDMU are roughly equivalent. At both locations the transformation rate of DDNU is 7–20 times that of the other steps. Estimated half-lives of DDE at stations 3C and 6C based on the M-SRS model results are ~19 and 72 years, respectively.

California↗

USGS2018

DDT and related compounds in pore water of shallow sediments on the Palos Verdes Shelf, California, USA

For nearly two and a half decades following World War II, production wastes from the world's largest manufacturer of technical DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene) were discharged into sewers of Los Angeles County. Following treatment, the wastes were released via a submarine outfall system to nearshore coastal waters where a portion accumulated in shallow sediments of the Palos Verdes Shelf (PVS). An investigation of the pore-water geochemistry of DDT-related compounds (DDX) was undertaken in an effort to understand factors controlling the rate of reductive dechlorination (RDC) of the major DDT degradate, 4,4′-DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene). Equilibrium matrix-solid phase microextraction (matrix-SPMEeq) combined with automated thermal desorption-gas chromatography/mass spectrometry (TDGC/MS) was used to determine freely dissolved concentrations of ten DDX analytes in sediment cores collected from three locations on the PVS (stations 3C, 6C, 8C, which are 7 km, 2 km, and 0 km, respectively, downcurrent from the outfall system). Pore-water concentrations (pM) of the principal DDX compounds involved in RDC were: 3C-DDE: 6.0–24, DDMU (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene): 11–160, DDNU (1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene): 1.8–68; 6C-DDE: 5.6–170, DDMU: 5.6–177, DDNU: 1.7–87; 8CDDE: 27–212, DDMU: 31–403, DDNU: 5.5–89. Variations in the spatial distribution of DDX analytes in pore water reflect several factors including proximity to the outfalls, RDC reaction rates, and natural variability in sedimentation and post-depositional transport processes. A comparison of pore-water data produced using matrix-SPME eq /TD-GC/MS and whole-core squeezing/solvent extraction/liquid injection-GC/MS indicates that the majority of the DDE in the upper sediment column (≤about 10 cm) is associated with dissolved/colloidal organic matter. Below that depth, freely-dissolved DDE predominates. The principal organic geochemical phase controlling sorption of DDE in PVS sediments are residual hydrocarbons, the vast majority of which originated from petroleum refinery wastes. Organic carbon-normalized sediment-water distribution coefficients (KOC) were calculated from solid-phase and pore-water concentrations of DDX and organic carbon. Log K OC values (L/kg) were relatively invariant across the shelf and with depth in the sediment column. Shelf-wide compound-specific coefficients (log K OC ) were: DDE: 7.5 ± 0.11, DDMU: 6.92 ± 0.13, DDNU: 6.37 ± 0.19. The spatial uniformity of K OC means that biological exposure and availability of the DDX compounds can, in principle, be estimated from solid-phase chemical measurements.

California↗

USGS2018

Deciphering the dynamics of inorganic carbon export from intertidal salt marshes using high-frequency measurements

The lateral export of carbon from coastal marshes via tidal exchange is a key component of the marsh carbon budget and coastal carbon cycles. However, the magnitude of this export has been difficult to accurately quantify due to complex tidal dynamics and seasonal cycling of carbon. In this study, we use in situ , high-frequency measurements of dissolved inorganic carbon (DIC) and water fluxes to estimate lateral DIC fluxes from a U.S. northeastern salt marsh. DIC was measured by a CHANnelized Optical Sensor (CHANOS) that provided an in situ concentration measurement at 15-min intervals, during periods in summer (July – August) and late fall (December). Seasonal changes in the marsh had strong effects on DIC concentrations, while tidally-driven water fluxes were the fundamental vehicle of marsh carbon export. Episodic events, such as groundwater discharge and mean sea water level changes, can impact DIC flux through altered DIC concentrations and water flow. Variability between individual tides within each season was comparable to mean variability between the two seasons. Estimated mean DIC fluxes based on a multiple linear regression (MLR) model of DIC concentrations and high-frequency water fluxes agreed reasonably well with those derived from CHANOS DIC measurements for both study periods, indicating that high-frequency, modeled DIC concentrations, coupled with continuous water flux measurements and a hydrodynamic model, provide a robust estimate of DIC flux. Additionally, an analysis of sampling strategies revealed that DIC fluxes calculated using conventional sampling frequencies (hourly to two-hourly) of a single tidal cycle are unlikely to capture a representative mean DIC flux compared to longer-term measurements across multiple tidal cycles with sampling frequency on the order of tens of minutes. This results from a disproportionately large amount of the net DIC flux occurring over a small number of tidal cycles, while most tides have a near-zero DIC export. Thus, high-frequency measurements (on the order of tens of minutes or better) over the time period of interest are necessary to accurately quantify tidal exports of carbon species from salt marshes.

Marine Chemistry↗

USGS2000

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6–8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p , p ′-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60–70% of ΣDDT. The p , p -DDE/ p , p ′-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p , p ′-DDE is occurring. Approximately 9–23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p , p ′-DDE inventory that has been observed at the study site for the period 1981–1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 10 2 –10 3 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722–724.). This explains why the DDT composition (i.e. o , p ′-, p , p ′-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents/factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p , p ′-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.

California↗

USGS2002

Sources of terrestrially-derived organic carbon in lower Mississippi River and Louisiana shelf sediments: Implications for differential sedimentation and transport at the coastal margin

In this study, we examined the temporal and spatial variability of terrestrial organic carbon sources in lower Mississippi River and Louisiana shelf sediments (during 11 cruises over a 22-month period) to further understand the sorting dynamics and selective transport of vascular plant materials within the primary dispersal system of the river. Bulk ??13C values in lower river sediments ranged from -21.90??? to -24.64??? (mean=-23.20??1.09???), these values were generally more depleted than those found in shelf sediments (-22.5??? to -21.2???). The ??8 (??8 = sum of vanillyl, syringyl and cinnamyl phenols produced from the oxidation of 100 mg of organic carbon) values in the lower river ranged from 0.71 to 3.74 (mean = 1.78??0.23). While there was no significant relationship between ??8 and river discharge (p>0.05), the highest value occurred during peak discharge in April 1999-which corresponded to the highest observed C/N value of 17.41. The ??8 values on the shelf ranged from 0.68 to 1.36 (mean = 0.54??0.30) and were significantly lower (p <0.05) than the average value for lower river sediments. The range of S/V (syringyl/vanillyl) and C/V (cinnamyl/vanillyl) ratios on the shelf, 0.11 to 0.95 and 0.01 to 0.08, respectively, were similar to that found in the lower river. These low C/V ratios are indicative a mixture of woody and non-woody carbon sources. Recent work by Goni et al. [Nature 389 (1997) 275; Geochim. Cosmochim. Acta 62 (1998) 3055], which did not include sampling transects within the primary dispersal system of the Mississippi River, showed a non-woody vascular plant signature on the Louisiana shelf. This suggests that riverine-derived woody tissues preferentially settle out of the water column, in the lower river and inner shelf, prior to the selective dispersal of C3 versus C4 non-woody materials in other regions the shelf and slope. This works further demonstrates the importance of differential settlement of particles, sampling location within the dispersal system, and river discharge, when examining biogeochemical cycles in river-dominated margins. ?? 2002 Elsevier Science B.V. All rights reserved.

Marine Chemistry↗

USGS1999

The impact of human activities on sediments of San Francisco Bay, California: an overview

This note introduces a set of eight papers devoted to a detailed study of two sediment cores from San Francisco Bay with an overview of the region and a chronology of human activities. Data used in this study to constrain the range of sediment ages at different depths include , and concentrations in the sediment and the age of shell fragments. In order of first detectable appearance in the record, the indicators of contamination that were analyzed include PAHs>Hg>Ag, Cu, Pb, Zn>DDT, PCB>foraminiferal Cd/Ca. This study also documents a large memory effect for estuarine contamination caused by sediment mixing and resuspension. Once an estuary such as San Francisco Bay has been contaminated, decades must pass before contaminant levels in surface sediment will return to background levels, even if external contaminant inputs have been entirely eliminated.

California↗

USGS1999

Sediment chronology in San Francisco Bay, California, defined by 210 Pb, 234 Th, 137 Cs, and 239,340 Pu

Sediment chronologies based on radioisotope depth profiles were developed at two sites in the San Francisco Bay estuary to provide a framework for interpreting historical trends in organic compound and metal contaminant inputs. At Richardson Bay near the estuary mouth, sediments are highly mixed by biological and/or physical processes. Excess penetration ranged from 2 to more than 10 cm at eight coring sites, yielding surface sediment mixing coefficients ranging from 12 to 170 cm 2 /year. At the site chosen for contaminant analyses, excess activity was essentially constant over the upper 25 cm of the core with an exponential decrease below to the supported activity between 70 and 90 cm. Both and penetrated to 57-cm depth and have broad subsurface maxima between 33 and 41 cm. The best fit of the excess profile to a steady state sediment accumulation and mixing model yielded an accumulation rate of 0.825 g/cm 2 /year (0.89 cm/year at sediment surface), surface mixing coefficient of 71 cm 2 /year, and 33-cm mixed zone with a half-Gaussian depth dependence parameter of 9 cm. Simulations of and profiles using these parameters successfully predicted the maximum depth of penetration and the depth of maximum and activity. Profiles of successive 1-year hypothetical contaminant pulses were generated using this parameter set to determine the age distribution of sediments at any depth horizon. Because of mixing, sediment particles with a wide range of deposition dates occur at each depth. A sediment chronology was derived from this age distribution to assign the minimum age of deposition and a date of maximum deposition to a depth horizon. The minimum age of sediments in a given horizon is used to estimate the date of first appearance of a contaminant from its maximum depth of penetration. The date of maximum deposition is used to estimate the peak year of input for a contaminant from the depth interval with the highest concentration of that contaminant. Because of the extensive mixing, sediment-bound constituents are rapidly diluted with older material after deposition. In addition, contaminants persist in the mixed zone for many years after deposition. More than 75 years are required to bury 90% of a deposited contaminant below the mixed zone. Reconstructing contaminant inputs is limited to changes occurring on a 20-year time scale. In contrast, mixing is much lower relative to accumulation at a site in San Pablo Bay. Instead, periods of rapid deposition and/or erosion occurred as indicated by frequent sand-silt laminae in the X-radiograph. , , and excess activity all penetrated to about 120 cm. The distinct maxima in the fallout radionuclides at 105–110 cm yielded overall linear sedimentation rates of 3.9 to 4.1 cm/year, which are comparable to a rate of 4.5±1.5 cm/year derived from the excess profile.

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