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1.
Chemosphere ; 354: 141713, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38490613

ABSTRACT

Historical pesticide use in agriculture and trace metal accumulation have long term impact on soil, sediment, and water quality. This research quantifies legacy and current-use pesticides and trace metals, assessing their occurrence and toxicological implications on a watershed scale in the Sogamoso River basin, tributary of the Magdalena River in Colombia. Organochlorine pesticides (22), organophosphates (7), and azole fungicides (5), as well as trace metals cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb), and zinc (Zn) were analyzed in croplands and along the river. Toxic units (TU) and hazard quotients (HQ) were calculated to assess the mixture toxicity. Organochlorines were detected in 84% of soils, 100% of sediments, and 80% of water samples. Organophosphates were found in 100% of soil and sediment samples, as well as in 70% of water samples. Azole fungicides were present in 79% of soils, 60% of sediments, and in 10% of water samples. Total pesticide concentrations ranged from 214.2 to 8497.7 µg/kg in soils, 569.6-12768.2 µg/kg in sediments, and 0.2-4.1 µg/L in water. In addition, the use of partition coefficient (Kd) and organic carbon fraction (foc) allowed the distribution analysis for most of the pesticides in sediments, suspended particulate matter (SPM), and water systems, but not for soils. Concentrations of trace metals Cu, Zn, Pb, and Zn exceeded international quality guidelines for agricultural soils in 16% of the samples. Furthermore, Cu and Zn concentrations exceeded sediment quality guidelines in 50 and 90% of the samples, respectively. These findings demonstrate the broad distribution of complex mixtures of trace metals, legacy organochlorines, and current-use pesticides across the basin, indicating that conventional agriculture is a significant source of diffuse pollution. Sustainable agricultural practices are needed to mitigate adverse impacts on ecosystems and human health.


Subject(s)
Fungicides, Industrial , Metals, Heavy , Pesticides , Trace Elements , Humans , Soil , Metals, Heavy/analysis , Pesticides/analysis , Ecosystem , Rivers , Fungicides, Industrial/analysis , Colombia , Lead/analysis , Environmental Monitoring , Trace Elements/analysis , Agriculture , Zinc/analysis , Azoles/analysis , Organophosphates , Geologic Sediments , Risk Assessment , China
2.
Curr Opin Nephrol Hypertens ; 33(1): 122-129, 2024 Jan 01.
Article in English | MEDLINE | ID: mdl-37889529

ABSTRACT

PURPOSE OF REVIEW: Geographically localized areas with a high prevalence of kidney disease exist currently in several regions of the world. Although the exact cause is unclear, environmental exposures accelerated by climate change, particularly heat exposure and ground water contamination, are hypothesized as putative risk factors. Aiming to inform investigations of water-related exposures as risk factors for kidney disease, we excavate the history of major water sources in three regions that are described as hotspots of kidney disease: the low-lying coastal regions in El Salvador and Nicaragua, the dry central region in Sri Lanka, and the Central Valley of California. RECENT FINDINGS: Historic data indicate that these regions have experienced water scarcity to which several human-engineered solutions were applied; these solutions could be hypothesized to increase residents' exposure to putative kidney toxins including arsenic, fluoride, pesticides, and cyanobacteria. Combined with heat stress experienced in context of climate change, there is potential for multistressor effects on kidney function. Climate change will also amplify water scarcity, and even if regional water sources are not a direct risk factor for development of kidney disease, their scarcity will complicate the treatment of the relatively larger numbers of persons with kidney disease living in these hotspots. SUMMARY: Nephrologists and kidney disease researchers need to engage in systematic considerations of environmental exposures as potential risk factors for kidney disease, including water sources, their increasing scarcity, and threats to their quality due to changing climate.


Subject(s)
Renal Insufficiency, Chronic , Humans , Renal Insufficiency, Chronic/etiology , Disease Hotspot , Environmental Exposure/adverse effects , Water , Kidney
3.
Environ Sci Technol ; 57(48): 19066-19077, 2023 Dec 05.
Article in English | MEDLINE | ID: mdl-37943968

ABSTRACT

Pollution by chemicals and waste impacts human and ecosystem health on regional, national, and global scales, resulting, together with climate change and biodiversity loss, in a triple planetary crisis. Consequently, in 2022, countries agreed to establish an intergovernmental science-policy panel (SPP) on chemicals, waste, and pollution prevention, complementary to the existing intergovernmental science-policy bodies on climate change and biodiversity. To ensure the SPP's success, it is imperative to protect it from conflicts of interest (COI). Here, we (i) define and review the implications of COI, and its relevance for the management of chemicals, waste, and pollution; (ii) summarize established tactics to manufacture doubt in favor of vested interests, i.e., to counter scientific evidence and/or to promote misleading narratives favorable to financial interests; and (iii) illustrate these with selected examples. This analysis leads to a review of arguments for and against chemical industry representation in the SPP's work. We further (iv) rebut an assertion voiced by some that the chemical industry should be directly involved in the panel's work because it possesses data on chemicals essential for the panel's activities. Finally, (v) we present steps that should be taken to prevent the detrimental impacts of COI in the work of the SPP. In particular, we propose to include an independent auditor's role in the SPP to ensure that participation and processes follow clear COI rules. Among others, the auditor should evaluate the content of the assessments produced to ensure unbiased representation of information that underpins the SPP's activities.


Subject(s)
Conflict of Interest , Ecosystem , Humans , Environmental Pollution , Biodiversity
4.
Artif Intell Earth Syst ; 2(3): 1-20, 2023 Jul 01.
Article in English | MEDLINE | ID: mdl-37841557

ABSTRACT

Tributary phosphorus (P) loads are one of the main drivers of eutrophication problems in freshwater lakes. Being able to predict P loads can aid in understanding subsequent load patterns and elucidate potential degraded water quality conditions in downstream surface waters. We demonstrate the development and performance of an integrated multimedia modeling system that uses machine learning (ML) to assess and predict monthly total P (TP) and dissolved reactive P (DRP) loads. Meteorological variables from the Weather Research and Forecasting (WRF) Model, hydrologic variables from the Variable Infiltration Capacity model, and agricultural management practice variables from the Environmental Policy Integrated Climate agroecosystem model are utilized to train the ML models to predict P loads. Our study presents a new modeling methodology using as testbeds the Maumee, Sandusky, Portage, and Raisin watersheds, which discharge into Lake Erie and contribute to significant P loads to the lake. Two models were built, one for TP loads using 10 environmental variables and one for DRP loads using nine environmental variables. Both models ranked streamflow as the most important predictive variable. In comparison with observations, TP and DRP loads were predicted very well temporally and spatially. Modeling results of TP loads are within the ranges of those obtained from other studies and on some occasions more accurate. Modeling results of DRP loads exceed performance measures from other studies. We explore the ability of both ML-based models to further improve as more data become available over time. This integrated multimedia approach is recommended for studying other freshwater systems and water quality variables using available decadal data from physics-based model simulations.

5.
Environ Sci Technol ; 57(35): 13056-13066, 2023 09 05.
Article in English | MEDLINE | ID: mdl-37603456

ABSTRACT

Estuaries are an important food source for the world's growing population, yet human health is at risk from elevated exposure to methylmercury (MeHg) via the consumption of estuarine fish. Moreover, the sources and cycling of MeHg in temperate estuarine ecosystems are poorly understood. Here, we investigated the seasonal and tidal patterns of mercury (Hg) forms in Long Island Sound (LIS), in a location where North Atlantic Ocean waters mix with the Connecticut River. We found that seasonal variations in Hg and MeHg in LIS followed the extent of riverine Hg delivery, while tides further exacerbated the remobilization of earlier deposited riverine Hg. The net production of MeHg near the river plume was significant compared to that in other locations and enhanced during high tide, possibly resulting from the enhanced microbial activity and organic carbon remineralization in the river plume. Statistical models, driven by our novel data, further support the hypothesis that the river-delivered organic matter and inorganic Hg drive net MeHg production in the estuarine water column. Our study sheds light on the significance of water column biogeochemical processes in temperate tidal estuaries in regulating MeHg levels and inspires new questions in our quest to understand MeHg sources and dynamics in coastal oceans.


Subject(s)
Mercury , Methylmercury Compounds , Animals , Humans , Estuaries , Ecosystem , Atlantic Ocean
6.
Kidney Int Rep ; 8(7): 1430-1438, 2023 Jul.
Article in English | MEDLINE | ID: mdl-37441476

ABSTRACT

Introduction: Chronic kidney disease of uncertain etiology (CKDu) is a leading cause of death of adults in Sri Lanka's dry region. Methods: We initiated the Kidney Progression Project (KiPP) to prospectively follow 292 persons with Chronic Kidney Disease Epidemiology Collaboration estimated glomerular filtration rate (eGFR) 20 to 60 ml/min per 1.73 m2 living in a CKDu endemic area. Using data from 3-year follow-up, we assessed kidney function decline (>30% from baseline eGFR), and the composite outcome of >30% eGFR decline, eGFR <15 ml/min or death, and explored the association of the 2 outcomes with baseline demographic, residential, and clinical parameters accounting for baseline eGFR. Results: Median eGFR at enrollment was 28 ml/min among 71 women; 30 ml/min among 221 men; 91% to 99% had trace or no proteinuria during follow-up. At enrollment, median serum sodium, uric acid, and potassium were 143 mmol/l, 6.3 mg/dl, 4.5 meq/l, respectively among women; and 143 mmol/l, 6.9 mg/dl, 4.3 meq/l among men. Mean slope of eGFR decline was -0.5 (SD 4.9) ml/min/yr. In exploratory analyses, men with greater years of education and those living in northern region of the study area experienced lower likelihood of disease progression (hazard ratios [HR] 0.87 [0.77-0.98] per additional year and 0.33 [0.12-0.89] for northern versus other subregions, respectively). There was a suggestion that men drinking well water had higher likelihood and men living further away from reservoirs had lower likelihood of >30% decline in eGFR (HR 2.07 [0.95-4.49] for drinking well water versus not, and HR 0.58 [0.32-1.05] per kilometer distance, respectively). Conclusions: The overall rate of kidney function decline was slow in this CKDu cohort, similar to other nonalbuminuric CKD, and event rates were similar among men and women. Further etiologic investigations could focus on specific residence locale and water use.

8.
Glob Chang Biol ; 29(12): 3240-3255, 2023 06.
Article in English | MEDLINE | ID: mdl-36943240

ABSTRACT

Climate change, biodiversity loss, and chemical pollution are planetary-scale emergencies requiring urgent mitigation actions. As these "triple crises" are deeply interlinked, they need to be tackled in an integrative manner. However, while climate change and biodiversity are often studied together, chemical pollution as a global change factor contributing to worldwide biodiversity loss has received much less attention in biodiversity research so far. Here, we review evidence showing that the multifaceted effects of anthropogenic chemicals in the environment are posing a growing threat to biodiversity and ecosystems. Therefore, failure to account for pollution effects may significantly undermine the success of biodiversity protection efforts. We argue that progress in understanding and counteracting the negative impact of chemical pollution on biodiversity requires collective efforts of scientists from different disciplines, including but not limited to ecology, ecotoxicology, and environmental chemistry. Importantly, recent developments in these fields have now enabled comprehensive studies that could efficiently address the manifold interactions between chemicals and ecosystems. Based on their experience with intricate studies of biodiversity, ecologists are well equipped to embrace the additional challenge of chemical complexity through interdisciplinary collaborations. This offers a unique opportunity to jointly advance a seminal frontier in pollution ecology and facilitate the development of innovative solutions for environmental protection.


Subject(s)
Ecosystem , Environmental Pollution , Biodiversity , Ecology , Conservation of Natural Resources , Climate Change
10.
Environ Sci Technol ; 55(2): 941-951, 2021 01 19.
Article in English | MEDLINE | ID: mdl-33400860

ABSTRACT

Seasonal hypoxia is a serious threat to coastal ecosystems. This study on hypoxia in Long Island Sound (LIS), a large urbanized estuary, focuses on responses to managed nitrogen load reductions and climate change. At the analyzed station in western LIS, warming in bottom waters (0.8 °C per decade) favors hypoxia. Total nitrogen concentrations have decreased (0.06 mg L-1 per decade) with load reductions, but no linear temporal trend in chlorophyll is discernible. Bottom dissolved oxygen has increased (0.48 mg L-1 per decade), despite warming-induced solubility decreases (0.13 mg L-1 per decade). Decreasing trends in hypoxic area and volume (100 km2 and 1 km3 per decade) reflect improved conditions and are coincident with reducing loads. Regressions link hypoxic extent to nitrogen loads, chlorophyll, salinity, and winds. Though mitigation has reduced hypoxia, these improvements will not be sustained in the warming climate without continued intervention. The warming-induced oxygen solubility decrease forecasted for 2099 (0.4 mg L-1) would erode 35% of the observed oxygen gains. Implementing a nitrogen load reduction of 1.2 × 106 kg year-1 before the century's end would offset the oxygen solubility decline. This overall approach is applicable to areas experiencing warming and continued development that complicate efforts to reign in hypoxia.


Subject(s)
Ecosystem , Estuaries , Climate Change , Humans , Hypoxia , Oxygen/analysis
11.
J Great Lakes Res ; 47(6): 1656-1670, 2021 Dec 13.
Article in English | MEDLINE | ID: mdl-35967967

ABSTRACT

Eutrophication and excessive algal growth pose a threat on aquatic organisms and the health of the public, environment, and the economy. Understanding what drives excessive algal growth can inform mitigation measures and aid in advance planning to minimize impacts. We demonstrate how simulated data from weather, hydrological, and agroecosystem numerical prediction models can be combined with machine learning (ML) to assess and predict Chlorophyll a (Chl a) concentrations, a proxy for lake eutrophication and algal biomass. The study area is Lake Erie for a 16-year period, 2002-2017. A total of 20 environmental variables from linked and coupled physical models are used as input features to train the ML model with Chl a observations from 16 measuring stations. Included are meteorological variables from the Weather Research and Forecasting (WRF) model, hydrological variables from the Variable Infiltration Capacity (VIC) model, and agricultural management practice variables from the Environmental Policy Integrated Climate (EPIC) agroecosystem model. The consolidation of these variables is conducive to a successful prediction of Chl a. Aside from the synergistic effects that weather, hydrology, and fertilizers have on eutrophication and excessive algal growth, we found that the application of different forms of both P and N fertilizers are highly ranked for the prediction of Chl a concentration. The developed ML model successfully predicts Chl a with a coefficient of determination of 0.81, bias of -0.12 µg/l and RMSE of 4.97 µg/l. The developed ML-based modeling approach can be used for impact assessment of agriculture practices in a changing climate that affect Chl a concentrations in Lake Erie.

12.
Sci Total Environ ; 745: 140800, 2020 Nov 25.
Article in English | MEDLINE | ID: mdl-32721618

ABSTRACT

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 15N 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 15N-RDX. The majority of RDX transformation in the water column was by mineralization to inorganic N (dissolved and evaded; 64%-78% of transformed 15N-RDX). RDX was mineralized primarily to N2O (62-74% of transformed 15N-RDX) and secondarily to N2 (1-2% of transformed 15N-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 15N derived from RDX onto sediment and suspended particulates was negligible in the overall mass balance of RDX transformation (2%-3% of transformed 15N-RDX). The fraction of 15N 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.

14.
Glob Public Health ; 14(2): 214-226, 2019 02.
Article in English | MEDLINE | ID: mdl-30095037

ABSTRACT

Over the last two decades, a global epidemic of chronic kidney disease of unknown etiology (CKDu) has emerged in rural, arid, agricultural, lowland areas. Endemic regions have reported 15 to 20% prevalence among residents aged 30-60 years. CKDu is a progressive and irreversible disease resulting in renal failure and death in the absence of dialysis or a kidney transplant. While much of the research has focused on identifying etiology, this project seeks to ascertain factors associated with the rapidity of kidney disease progression in one of Sri Lanka's CKDu endemic areas. A sample of 296 male and female residents aged 21 to 65 with moderate CKD, as measured by their serum creatinine level, and a clinical diagnosis of CKDu are followed using quarterly serum testing to track the rate of progression. A baseline survey administered to the entire sample addresses potential risk factors, supplemented by a short survey focusing on changes through time. Concurrently water, soil and air are tested at the local and household levels. The study is the first to foster a multi-disciplinary approach that focuses on disease progression, identifying behavioural and exposure risk factors for rapid kidney function decline, in this progressively fatal disease.


Subject(s)
Disease Progression , Renal Insufficiency, Chronic/epidemiology , Renal Insufficiency, Chronic/etiology , Adult , Aged , Female , Health Surveys , Humans , Longitudinal Studies , Male , Middle Aged , Prevalence , Renal Insufficiency, Chronic/diagnosis , Rural Population , Sri Lanka/epidemiology , Young Adult
15.
Sci Total Environ ; 647: 369-378, 2019 Jan 10.
Article in English | MEDLINE | ID: mdl-30086489

ABSTRACT

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 15N 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 N2) 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 15N as RDX (15N-[RDX]) equivalents after 21 days. Measured nitroso-triazines in the aquaria accounted for 6-13% of total added 15N-[RDX]. 15N-labeled DIN was found both in the oxic surface water and hypoxic porewaters, showing that RDX mineralization accounted for 34% of the 15N-[RDX] added to the aquaria over 21 days. Labeled ammonium (15NH4+, found in sediment and overlying water) and nitrate + nitrite (15NOX, found in overlying water only) together represented 10% of the total added 15N-[RDX]. The production of 15N labeled N2 (15N2), accounted for the largest individual sink during the transformation of the total added 15N-[RDX] (25%). Hypoxic sediment was the most favorable zone for production of N2, most of which diffused through porous sediments into the water column and escaped to the atmosphere.

16.
Environ Pollut ; 243(Pt A): 453-461, 2018 Dec.
Article in English | MEDLINE | ID: mdl-30212799

ABSTRACT

Perfluoroalkyl acids (PFAAs) were measured in aqueous and suspended particulate matter (SPM) fractions in the final effluents from 12 wastewater treatment facilities located around the Connecticut shoreline. Aqueous phase concentrations ranged from 53 to 198 ng/L for ∑PFAAs with ≤7 perfluorinated carbons (CF2) and 2-73 ng/L for >7 CF2 PFAAs. Predominant PFAAs associated with effluent derived SPM were perfluorodecanoic acid and perflurorooctane sulfonic acid, detected in 48% and 52% of samples in concentrations ranging from 7 CF2 PFAAs. Partitioning coefficients (log KOC) derived for effluent water and SPM phases (4.2 ±â€¯0.3, 4.4 ±â€¯0.4, 5.1 ±â€¯0.2 and 5.3 ±â€¯0.2 for PFOA, PFNA PFDA and PFUnA; 4.5 ±â€¯0.2 and 5.2 ±â€¯0.2 for PFOS and PFHsX respectively) were found to be of similar magnitude to aeration tank particles, though 0.5 to 2 log units greater than sludge solids and to natural system particulates including riverine SPM, estuarine SPM and sediments. Results from this study suggest that effluent derived suspended particulate matter could be an effective vector in the transport of long-chained PFAAs through wastewater treatment into receiving waters, and a potential vector to the local food chain.


Subject(s)
Alkanesulfonic Acids/analysis , Decanoic Acids/analysis , Fluorocarbons/analysis , Particulate Matter/chemistry , Wastewater/chemistry , Environmental Monitoring , New York , Particle Size , Sewage , Water Pollutants, Chemical/analysis
17.
Environ Toxicol Chem ; 37(7): 1990-1997, 2018 07.
Article in English | MEDLINE | ID: mdl-29603346

ABSTRACT

Over the last century, unexploded ordnances have been disposed of in marine shelf systems because of a lack of cost-effective alternatives. Underwater unexploded ordnances have the potential to leak 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-triazine (RDX), commonly used chemical munitions, and contaminate local waters, biota, and sediments. The rate at which this contamination occurs in the environment is relatively unknown, and the cost- and time-prohibitive nature of sampling across sites makes mapping difficult. In the present study we assessed the efficacy of ethylene-vinyl acetate (EVA) for sampling relatively soluble munitions compounds over a range of environmental conditions (i.e., changes in temperature and salinity) and optimized the composition of the passive sampling polymer. The EVA sampler was able to successfully detect ambient concentrations of lingering munitions compounds from field sites containing unexploded ordnances. The sampler affinity for the munitions in terms of an EVA-water partition coefficient was greater than the standard octanol water values for each target compound. Partitioning of compounds onto EVA over the natural ranges of salinity did not change significantly, although uptake varied consistently and predictably with temperature. Increasing the vinyl acetate to ethylene ratio of the polymer corresponded to an increase in uptake capacity, consistent with enhanced dipole-dipole interactions between the munitions and the polymer. This sampler provides a cost-effective means to map and track leakage of unexploded ordnances both spatially and temporally. Environ Toxicol Chem 2018;37:1990-1997. © 2018 SETAC.


Subject(s)
Environmental Monitoring/instrumentation , Explosive Agents/analysis , Fresh Water/chemistry , Seawater/chemistry , Acetates/analysis , Entropy , Kinetics , Salinity , Temperature , Thermodynamics , Triazines/analysis , Trinitrotoluene/analysis , Water Pollutants, Chemical/analysis
18.
Environ Toxicol Chem ; 36(5): 1170-1180, 2017 05.
Article in English | MEDLINE | ID: mdl-27791286

ABSTRACT

The lack of knowledge on the fate of explosive compounds 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), particularly in marine ecosystems, constrains the application of bioremediation techniques in explosive-contaminated coastal sites. The authors present a comparative study on anaerobic biodegradation and mineralization of 15 N-nitro group isotopically labeled TNT and RDX in organic carbon-rich, fine-grained marine sediment with native microbial assemblages. Separate sediment slurry experiments were carried out for TNT and RDX at 23°C for 16 d. Dissolved and sediment-sorbed fractions of parent and transformation products, isotopic compositions of sediment, and mineralization products of the dissolved inorganic N pool (15 NH4+ ,15 NO3- ,15 NO2- , and 15 N2 ) were measured. The rate of TNT removal from the aqueous phase was faster (0.75 h-1 ) than that of RDX (0.37 h-1 ), and 15 N accumulation in sediment was higher in the TNT (13%) than the RDX (2%) microcosms. Mono-amino-dinitrotoluenes were identified as intermediate biodegradation products of TNT. Two percent of the total spiked TNT-N is mineralized to dissolved inorganic N through 2 different pathways: denitration as well as deamination and formation of NH4+ , facilitated by iron and sulfate reducing bacteria in the sediments. The majority of the spiked TNT-N (85%) is in unidentified pools by day 16. Hexahydro-1,3,5-trinitro-1,3,5-triazine (10%) biodegrades to nitroso derivatives, whereas 13% of RDX-N in nitro groups is mineralized to dissolved inorganic N anaerobically by the end of the experiment. The primary identified mineralization end product of RDX (40%) is NH4+ , generated through either deamination or mono-denitration, followed by ring breakdown. A reasonable production of N2 gas (13%) was seen in the RDX system but not in the TNT system. Sixty-eight percent of the total spiked RDX-N is in an unidentified pool by day 16 and may include unquantified mineralization products dissolved in water. Environ Toxicol Chem 2017;36:1170-1180. © 2016 SETAC.


Subject(s)
Explosive Agents/metabolism , Geologic Sediments/chemistry , Triazines/metabolism , Trinitrotoluene/metabolism , Biodegradation, Environmental , Explosive Agents/chemistry , Isotope Labeling , Nitrogen Isotopes/chemistry , Principal Component Analysis , Triazines/chemistry , Trinitrotoluene/chemistry , Water/chemistry
19.
Chemosphere ; 153: 28-38, 2016 Jun.
Article in English | MEDLINE | ID: mdl-27010164

ABSTRACT

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is globally one of the most commonly used military explosives and environmental contaminant. (15)N labeled RDX was added into a mesocosm containing 9 different coastal marine species in a time series experiment to quantify the uptake of RDX and assess the RDX derived (15)N retention into biota tissue. The (15)N attributed to munitions compounds reached steady state concentrations ranging from 0.04 to 0.67 µg (15)N g dw(-1), the bulk (15)N tissue concentration for all species was 1-2 orders of magnitude higher suggesting a common mechanism or pathway of RDX biotransformation and retention of (15)N. A toxicokinetic model was created that described the (15)N uptake, elimination, and transformation rates. While modeled uptake rates were within previous published values, elimination rates were several orders of magnitude smaller than previous studies ranging from 0.05 to 0.7 days(-1). These small elimination rates were offset by high rates of retention of (15)N previously not measured. Bioconcentration factors and related aqueous:organism ratios of compounds and tracer calculated using different tracer and non-tracer methods yielded a broad range of values (0.35-101.6 mL g(-1)) that were largely method dependent. Despite the method-derived variability, all values were generally low and consistent with little bioaccumulation potential. The use of (15)N labeled RDX in this study indicates four possible explanations for the observed distribution of compounds and tracer; each with unique potential implications for possible toxicological impacts in the coastal marine environment.


Subject(s)
Aquatic Organisms/metabolism , Biota , Explosive Agents/metabolism , Nitrogen Isotopes/chemistry , Triazines/metabolism , Aquatic Organisms/chemistry , Biotransformation , Explosive Agents/chemistry , Kinetics , Nitrogen Isotopes/metabolism , Triazines/chemistry
20.
Environ Toxicol Chem ; 35(1): 47-55, 2016 Jan.
Article in English | MEDLINE | ID: mdl-26178383

ABSTRACT

Examination of the partitioning of explosives onto sediment in marine environments is critical to predict the toxicological impacts of worldwide explosive-contaminated sites adjacent to estuaries, wetlands, and the coastal ocean. Marine sediments have been identified as sites of enhanced munitions removal, yet most studies addressing these interactions focus on soils and freshwater sediments. The present study measured the kinetics of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) sorption onto 2 marine sediments of varying grain sizes (silt vs sand) and organic carbon (OC) content. Abiotic sediment sorption tests were performed at 23 °C, 15 °C, and 4 °C by spiking TNT and RDX solutions directly into anaerobic sediment slurries. Marine sediments showed significantly higher compound uptake rates (0.30-0.80 h(-1) ) than freshwater silt (0.0046-0.0065 h(-1) ) for both compounds, probably because of lower compound solubilities and a higher pH in marine systems. Equilibrium partition constants are on the same order of magnitude for marine silt (1.1-2.0 L kg(-1) sediment) and freshwater silt (1.4-3.1 L kg(-1) sediment) but lower for marine sand (0.72-0.92 L kg(-1) sediment). Total organic carbon content in marine sediments varied linearly with equilibrium partition constants for TNT and was moderately linear for RDX. Uptake rates and equilibrium constants of explosives are inversely correlated to temperature regardless of sediment type because of kinetic barriers associated with low temperatures.


Subject(s)
Explosive Agents/chemistry , Geologic Sediments/analysis , Triazines/chemistry , Trinitrotoluene/chemistry , Adsorption , Algorithms , Anaerobiosis , Carbon/analysis , Explosive Agents/analysis , Fresh Water/chemistry , Hydrogen-Ion Concentration , Kinetics , Particle Size , Temperature , Triazines/analysis , Trinitrotoluene/analysis , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry
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