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Richard W. Smith

Publications and source records attributed to Richard W. Smith.

4 recordsLinked to original sources

Degradation of RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine) in contrasting coastal marine habitats: Subtidal non-vegetated (sand), subtidal vegetated (silt/eel grass), and intertidal marsh

Hundreds of explosive-contaminated marine sites exist globally, many of which contain the common munitions constituent hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Quantitative information about RDX transformation in coastal ecosystems is essential for management of many of these sites. Isotopically labelled RDX containing 15 N in all 3 nitro groups was used to track the fate of RDX in three coastal ecosystem types. Flow-through mesocosms representing subtidal vegetated (silt/eel grass), subtidal non-vegetated (sand) and intertidal marsh ecosystems were continuously loaded with isotopically labelled RDX for 16–17 days. Sediment, pore-water and overlying surface water were analyzed to determine the distribution of RDX, nitroso-triazine transformation products (NXs) and nitrogen containing complete mineralization products, including ammonium, nitrate+nitrite, nitrous oxide and nitrogen gas. The marsh, silt, and sand ecotypes transformed 94%, 90% and 76% of supplied RDX, respectively. Total dissolved NXs accounted for 2%–4% of the transformed 15 N-RDX. The majority of RDX transformation in the water column was by mineralization to inorganic N (dissolved and evaded; 64%–78% of transformed 15 N-RDX). RDX was mineralized primarily to N 2 O (62–74% of transformed 15 N-RDX) and secondarily to N 2 (1–2% of transformed 15 N-RDX) which exchanged with the atmosphere. Transformation of RDX was favored in carbon-rich lower redox potential sediments of the silt and marsh mesocosms where anaerobic processes of iron and sulfate reduction were most prevalent. RDX was most persistent in the carbon-poor sand mesocosm. Partitioning of 15 N derived from RDX onto sediment and suspended particulates was negligible in the overall mass balance of RDX transformation (2%–3% of transformed 15 N-RDX). The fraction of 15 N derived from RDX that was sorbed or assimilated in sediment was largest in the marsh mesocosm (most organic carbon), and smallest in the sand mesocosm (largest grain size and least organic carbon). Sediment redox conditions and available organic carbon stores affect the fate of RDX in different coastal marine habitats.

Connecticut, New York

Tracing the cycling and fate of the munition, Hexahydro-1,3,5-trinitro-1,3,5-triazine in a simulated sandy coastal marine habitat with a stable isotopic tracer, 15N-[RDX]

Coastal marine habitats become contaminated with the munitions constituent, Hexahydro-1,3,5-trinitro-1,3,5-trazine (RDX), via military training, weapon testing and leakage of unexploded ordnance. This study used 15 N labeled RDX in simulated aquarium-scale coastal marine habitat containing seawater, sediment, and biota to track removal pathways from surface water including sorption onto particulates, degradation to nitroso-triazines and mineralization to dissolved inorganic nitrogen (DIN). The two aquaria received continuous RDX inputs to maintain a steady state concentration (0.4 mg L −1 ) over 21 days. Time series RDX and nitroso-triazine concentrations in dissolved (surface and porewater) and sorbed phases (sediment and suspended particulates) were analyzed. Distributions of DIN species (ammonium, nitrate + nitrite and dissolved N 2 ) in sediments and overlying water were also measured along with geochemical variables in the aquaria. Partitioning of RDX and RDX-derived breakdown products onto surface sediment represented 13% of the total added 15 N as RDX ( 15 N-[RDX]) equivalents after 21 days. Measured nitroso-triazines in the aquaria accounted for 6–13% of total added 15 N-[RDX]. 15 N-labeled DIN was found both in the oxic surface water and hypoxic porewaters, showing that RDX mineralization accounted for 34% of the 15 N-[RDX] added to the aquaria over 21 days. Labeled ammonium ( 15 NH 4 + , found in sediment and overlying water) and nitrate + nitrite ( 15 NO X , found in overlying water only) together represented 10% of the total added 15 N-[RDX]. The production of 15 N labeled N 2 ( 15 N 2 ), accounted for the largest individual sink during the transformation of the total added 15 N-[RDX] (25%). Hypoxic sediment was the most favorable zone for production of N 2 , most of which diffused through porous sediments into the water column and escaped to the atmosphere.

Science of the Total Environment

Contribution of hurricane-induced sediment resuspension to coastal oxygen dynamics

Hurricanes passing over the ocean can mix the water column down to great depths and resuspend massive volumes of sediments on the continental shelves. Consequently, organic carbon and reduced inorganic compounds associated with these sediments can be resuspended from anaerobic portions of the seabed and re-exposed to dissolved oxygen (DO) in the water column. This process can drive DO consumption as sediments become oxidized. Previous studies have investigated the effect of hurricanes on DO in different coastal regions of the world, highlighting the alleviation of hypoxic conditions by extreme winds, which drive vertical mixing and re-aeration of the water column. However, the effect of hurricane-induced resuspended sediments on DO has been neglected. Here, using a diverse suite of datasets for the northern Gulf of Mexico, we find that in the few days after a hurricane passage, decomposition of resuspended shelf sediments consumes up to a fifth of the DO added to the bottom of the water column during vertical mixing. Despite uncertainty in this value, we highlight the potential significance of this mechanism for DO dynamics. Overall, sediment resuspension likely occurs over all continental shelves affected by tropical cyclones, potentially impacting global cycles of marine DO and carbon.

Scientific Reports

Tracing the cycling and fate of the explosive 2,4,6-trinitrotoluene in coastal marine systems with a stable isotopic tracer, 15N-[TNT]

2,4,6-Trinitrotoluene (TNT) has been used as a military explosive for over a hundred years. Contamination concerns have arisen as a result of manufacturing and use on a large scale; however, despite decades of work addressing TNT contamination in the environment, its fate in marine ecosystems is not fully resolved. Here we examine the cycling and fate of TNT in the coastal marine systems by spiking a marine mesocosm containing seawater, sediments, and macrobiota with isotopically labeled TNT ( 15 N-[TNT]), simultaneously monitoring removal, transformation, mineralization, sorption, and biological uptake over a period of 16 days. TNT degradation was rapid, and we observed accumulation of reduced transformation products dissolved in the water column and in pore waters, sorbed to sediments and suspended particulate matter (SPM), and in the tissues of macrobiota. Bulk δ 15 N analysis of sediments, SPM, and tissues revealed large quantities of 15 N beyond that accounted for in identifiable derivatives. TNT-derived N was also found in the dissolved inorganic N (DIN) pool. Using multivariate statistical analysis and a 15 N mass balance approach, we identify the major transformation pathways of TNT, including the deamination of reduced TNT derivatives, potentially promoted by sorption to SPM and oxic surface sediments.

Environmental Science & Technology