Persistent organic pollutants in the Atlantic and southern oceans and oceanic atmosphere

Persistent organic pollutants (POPs) continue to cycle through the atmosphere and hydrosphere despite banned or severely restricted usages. Global scale analyses of POPs are challenging, but knowledge of the current distribution of these compounds is needed to understand the movement and long-term consequences of their global use. In the current study, air and seawater samples were collected Oct. 2007–Jan. 2008 aboard the Icebreaker Oden en route from Göteborg, Sweden to McMurdo Station, Antarctica. Both air and surface seawater samples consistently contained α-hexachlorocyclohexane (α-HCH), γ-HCH, hexachlorobenzene (HCB), α-Endosulfan, and polychlorinated biphenyls (PCBs). Sample concentrations for most POPs in air were higher in the northern hemisphere with the exception of HCB, which had high gas phase concentrations in the northern and southern latitudes and low concentrations near the equator. South Atlantic and Southern Ocean seawater had a high ratio of α-HCH to γ-HCH, indicating persisting levels from technical grade sources. The Atlantic and Southern Ocean continue to be net sinks for atmospheric α-, γ-HCH, and Endosulfan despite declining usage

Levels, sources and chemical fate of persistent organic pollutants in the atmosphere and snow along the western Antarctic Peninsula

The Antarctic continent is among the most pristine regions; yet various organic contaminants have been measured there routinely. Air and snow samples were collected during the austral spring (October November, 2010) along the western Antarctic Peninsula and analyzed for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) to assess the relative importance of long-range transport versus local primary or secondary emissions. Highest concentrations of PCBs, PBDEs and DDTs were observed in the glacier\u27s snow sample, highlighting the importance of melting glaciers as a possible secondary source of legacy pollutants to the Antarctic. In the atmosphere, contaminants were mainly found in the vapor phase (\u3e65%). Hexachlorobenzene (33.6 pg/m(3)), PCBs (11.6 pg/m(3)), heptachlor (5.64 pg/m(3)), PBDEs (4.22 pg/m(3)) and cis-chlordane (2.43 pg/m(3)) were the most abundant contaminants. In contrast to other compounds, PBDEs seem to have originated from local sources, possibly the research station itself. Gas-particle partitioning for analytes were better predicted using the adsorption partitioning model than an octanol-based absorption approach. Diffusive flux calculations indicated that net deposition is the dominant pathway for PBDEs and chlordanes, whereas re-volatilization from snow (during melting or metamorphosis) was observed for PCBs and some OCPs. (C) 2016 Elsevier Ltd. All rights reserved

Geochemistry of redox-sensitive trace elements in a shallow subterranean estuary

Submarine groundwater discharge (SGD) is an important component of chemical fluxes in the coastal ocean. The composition of SGD is influenced by biogeochemical reactions that take place within the subterranean estuary (STE), the subsurface mixing zone of fresh and saline groundwaters. The STE is characterized by redox gradients that affect the speciation and mobility of redox-sensitive elements (RSEs). We examined the distributions and behavior of the RSEs Mo, U, V, and Cr within the larger redox framework of a shallow STE and evaluated the source-sink function of the STE for these elements. We found that the advection of water through the STE and the apparent respiration of organic matter drives the formation of a “classic” redox sequence typically observed in diffusion-dominated fine-grained sediments. High concentrations of dissolved organic matter (up to 2.9 mM) lead to extensive sulfide production (up to 1.8 mM) within 3 m of the surface. Both Mo and U are quantitatively removed as oxic surface waters mix into ferruginous and sulfidic zones. Molybdenum removal appears to occur where sulfide concentrations exceed ~ 11 μM, a previously reported threshold for quantitative formation of highly particle-reactive thiomolybdate species. Uranium removal apparently occurs via reduction and formation of insoluble phases or sorption to sediments. It is not clear how readily sequestered metals may be returned to solution, but SGD may be an important sink in the marine budget for both Mo and U. In contrast, both V and Cr show non-conservative addition across the salinity mixing gradient. Increases in pH appear to promote dissolution of V from minerals within the shallow aquifer, and mobilization may also be associated with dissolved organic matter. Chromium enrichment is associated with higher dissolved organic matter and is likely due to the formation of soluble Cr-organic complexes. Fluxes of these elements were constrained using SGD volume fluxes, determined using radium isotopes as well as direct discharge measurements by Lee-type seepage meters, and concentrations in directly-sampled seepage (Mo: − 0.21 to − 7.7 μmol m− 2 day− 1; U: − 0.02 to − 0.6 μmol m− 2 day− 1; V: 0.05 to 2.0 μmol m− 2 day− 1; Cr: 0.12 to 4.4 μmol m− 2 day− 1)

Chemical Flux Associated with Spatially and Temporally Variable Submarine Groundwater Discharge, and Chemical Modification in the Subterranean Estuary at Gloucester Point, VA (USA)

Submarine groundwater discharge represents a major but poorly constrained component of coastal marine chemical budgets. In the current study, the geochemical behavior of 224Ra, inorganic nitrogen species, and Fe in shallow coastal groundwater was characterized to improve estimates of chemical flux via submarine groundwater discharge (SGD) at a site in the York River estuary, VA (USA). Directly measured SGD rates varied between 3.9 ± 1.2 cm day−1 offshore, and 8.9 ± 2.6 cm day−1 close to shore. A clear inverse relationship was observed between SGD and tidal height, reflecting the hydraulic gradient between groundwater and surface water. Discharge rates varied spatially in conjunction with the subterranean estuary location, and there was a strong inverse correlation between seepage rates and seepage salinity. Dissolved 224Ra activity in the mixing zone reached levels up to 6 dpm L−1 and co-varied with salinity in the groundwater but not in the surface water or seepage water. Instead, a consistent sigmoidal trend of Ra with pH was observed, which matched previous laboratory experiment results. Dissolved NH4 + reached concentrations up to 120 μM in the groundwater and appeared to mix conservatively with respect to salinity in the subterranean estuary. In contrast, NOx (NO2 − + NO3 −) was low in both fresh groundwater and surface water and showed non-conservative enrichment (up to 23 μM) within the subterranean estuary. Dissolved Fe also showed non-conservative excess in the subterranean estuary, reaching concentrations up to 50 μM. SGD-derived chemical fluxes were estimated using several different commonly used approaches: average groundwater concentrations, pore water constituent-salinity trends coupled with directly collected seepage salinity, constituent concentrations in directly collected seepage, and concentrations in shallowest groundwater samples. Different flux estimates were compared with a “variable endmember” approach based on the observed geochemical distribution and inferred behavior

Effect of Photolysis on Absorption and Fluorescence Spectra of Light-Absorbing Secondary Organic Aerosols

Excitation–emission matrices (EEMs) constructed from fluorescence measurements are increasingly used for the characterization of chromophoric dissolved organic matter (CDOM) and light-absorbing atmospheric organic aerosols known as brown carbon (BrC). There is a high uncertainty in the effect of BrC aerosols on climate because their optical properties depend on the amount of time they spent in the atmosphere. In order to aid in the quantification of BrC aerosols’ contribution to radiative forcing, we investigated the effect of solar radiation on the fluorescence, expressed as EEMs, and absorption spectra of the water-soluble fraction of BrC species formed by the high-NOx photooxidation of benzene, toluene, p-xylene, and naphthalene. The BrC samples were prepared in a smog chamber, extracted in water, and irradiated in a solar simulator at a fixed pH of 3, representative of aerosol liquid water, or at a fixed pH of 6, representative of cloudwater. Semicontinuous fluorescence and absorbance measurements were carried out during the irradiation at 20 min intervals for 44 h. The absorption coefficients depended on the solution pH, with the solutions at pH 6 absorbing stronger than solutions at pH 3. All samples underwent a decrease in absorption coefficient at all visible wavelengths, whereas fluorescence intensities showed both increases and decreases in different regions of the EEMs. Upon comparison with CDOM samples, the fluorescence intensity of all secondary organic aerosol (SOA) samples decreased in the region of the EEMs where the characteristic terrestrial humic-like C peak occurs. These experimental observations suggest that (i) this type of BrC will have different effects on climate depending on whether it ends up in an acidic or neutral environment; (ii) exposure to UV radiation will diminish the ability of this type of BrC to affect climate on a time scale of about a day; (iii) fluorescence by BrC compounds has a minimal effect on aerosol radiative forcing; (iv) photooxidized aromatics may be closely related, in terms of optical properties, to CDOM found in fresh waters