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

Nelson W. Green; E. Michael Perdue; George R. Aiken; Kenna D. Butler; Hongmei Chen; Thorsten Dittmar; Jutta Niggemann; Aron Stubbins

doi:10.1016/j.marchem.2014.01.012

USGS · 70189561

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

Nelson W. Green·E. Michael Perdue·George R. Aiken·Kenna D. Butler·Hongmei Chen·Thorsten Dittmar·Jutta Niggemann·Aron Stubbins

View original source ↗Export metadata ↓

Abstract

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.

Explore related subjects

Marine Chemistry Article

Keep this discovery

Explore connections, maps & timelines

BibTeX RIS

Nelson W. Green, E. Michael Perdue, George R. Aiken, Kenna D. Butler, Hongmei Chen, Thorsten Dittmar, Jutta Niggemann, Aron Stubbins. 2014. An intercomparison of three methods for the large-scale isolation of oceanic dissolved organic matter. https://doi.org/10.1016/j.marchem.2014.01.012

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related USGS reports

USGS2022

The role of pH up-regulation in response to nutrient-enriched, low-pH groundwater discharge

Coral reefs and their ecosystems are threatened by both global stressors, including increasing sea-surface temperatures and ocean acidification (OA), and local stressors such as land-based sources of pollution that can magnify the effects of OA. Corals can physiologically control the chemistry of their internal calcifying fluids (CF) and can thereby regulate their calcification process. Specifically, increasing aragonite saturation state in the CF (Ω CF ) may allow corals to calcify even under external low saturation conditions. Questions remain regarding the physiological processes that govern the CF chemistry and how they change in response to multiple stressors. To address this knowledge gap, the boron δ 11 B and B/Ca were analyzed in tropical corals, Porites lobata, collected at submarine groundwater seeps impacted by the release of treated wastewater in west Maui, Hawai'i, to document the interactions between high nutrient / low pH seep water on CF carbonate chemistry. Results show substantial up-regulation of pH and dissolved inorganic carbon (DIC) with respect to seawater in P. lobata corals collected from within the wastewater impacted area at Kahekili Beach Park compared to the control site at Olowalu Beach. The Ω CF was 9 to 10 times higher than ambient seawater Ω, and 13 to 26% higher than in corals from the control site and from values previously observed in tropical Porites spp. corals. Such elevated up-regulation suggests that corals exposed to nutrient-enriched, low pH effluent sustain CF supersaturated with respect to aragonite, possibly as an internal coping mechanism to combat multiple stressors from land-based sources of pollution. This elevated up-regulation has implications to coral vulnerability to future climate- and ocean-change.

Hawaii↗

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↗