Toxicological and chemical assessment of ordinance compounds in marine sediments and porewaters

Toxicological and chemical studies were performed with a silty and a sandy marine sediment spiked with 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrophenylmethylnitramine (tetryl), or 2,4,6-trinitrophenol (picric acid). Whole sediment toxicity was analyzed by the 10-day survival test with the amphipod Ampelisca abdita, and porewater toxicity tests assessed macro-algae (Ulva fasciata) zoospore germination and germling growth, sea urchin (Arbacia punctulata) embryological development, and polychaete (Dinophilus gyrociliatus) survival and reproduction. Whole sediments spiked with 2,6-DNT were not toxic to amphipods. The fine-grained sediment spiked with tetryl was also not acutely toxic. The tetryl and picric acid LC50 values in the sandy sediment were 3.24 and 144 mg/kg dry weight, respectively. The fine-grained sediment spiked with picric acid generated a U-shaped concentration-response curve in the amphipod test, with increased survival both in the lowest and highest concentration. Grain-size distribution and organic carbon content strongly influenced the behavior of ordnance compounds in spiked sediments. Very low concentrations were measured in some of the treatments and irreversible binding and biodegradation are suggested as the processes responsible for the low measurements. Porewater toxicity varied with its sedimentary origin and with ordnance compound. The sea urchin embryological development test tended to be the least sensitive. Tetryl was the most toxic chemical in all porewater tests, and picric acid the least toxic. Samples spiked with 2,6-DNT contained a degradation product identified as 2-methyl-3-nitroaniline (also known as 2-amino-6-nitrotoluene), and unidentified peaks, possibly degradation products, were also seen in some of the picric acid- and tetryl-spiked samples. Degradation products may have played a role in observed toxicity.     

Fate and effects of picric acid and 2,6-DNT in marine environments: toxicity of degradation products

The toxicity of transformation products of 2,6-dinitrotoluene (2,6-DNT) and 2,4,6-trinitrophenol (picric acid) were assessed in spiked sandy and fine-grained marine sediments and in seawater. Toxicity of pore water from sediments spiked with 2,6-DNT decreased for the macro-alga, Ulva fasciata, zoospores as biotransformation proceeded, but increased for the copepod, Schizopera knabeni, nauplii. The primary biotransformation product of 2,6-DNT, 2-amino-6-nitrotoluene, was also more toxic than the parent compound to copepod nauplii, but not to alga zoospores, in spiked seawater tests. Two biotransformation products of picric acid, picramic acid and 2,4-DNP, were more toxic than their parent compound. Porewater toxicity from picric acid-spiked sediments decreased significantly at the end of six-months incubation. Fine-grained sediment spiked with either ordnance compound had lower toxicity than its sandy counterpart after six months, suggesting faster microbial transformation in the former and production of less toxic products. Photo-transformation of 2,6-DNT in seawater resulted in a reduction in toxicity.     

2,4,6-trinitrotoluene transformation by a tropical marine yeast, Yarrowia lipolytica NCIM 3589

Yarrowia lipolytica NCIM 3589, a tropical marine degrader of hydrocarbons and triglycerides transformed 2,4,6-trinitrotoluene (TNT) very efficiently. Though this yeast could not utilize TNT as the sole carbon or nitrogen source, it was capable of reducing the nitro groups in TNT to aminodinitrotoluene (ADNT). In a complete medium containing glucose and ammonium sulphate as the available carbon and nitrogen sources respectively, the culture was able to completely transform 1 mM (227 ppm) of TNT under such conditions. A dual pathway was found to be functional, one of which resulted in the formation of the hydride-Meisenheimer complex (H(-)TNT) as a transiently accumulating metabolite that was subsequently denitrated to 2,4-dinitrotoluene (2,4-DNT), whereas the other pathway resulted in the formation of amino derivatives. The presence of increasing amounts of reducing equivalents in the form of glucose promoted better growth and the nitroreductases of this yeast to reduce the aromatic ring to 2,4-DNT although, the reduction of the nitro groups to amino groups was the major functional pathway. The ability of this tropical marine yeast to transform TNT into products such as 2,4-DNT which in turn could be metabolized by other microbes has implications in the use of this yeast for bioremediation of TNT polluted marine environments.     

Methyltins in the marine environment

Methyltins were occasionally observed in some natural waters. The nature of a marine sediment determines its organotin burdens. Mono- and dimethyltin compounds were found in polluted marine sediments whereas non-polluted, oxiccoastal sediments contained primarily trimethyltin. The net methylation rate is evidently independent of the inorganic tin content of a sediment. Methyltin in fish is about 3–6% of the total tin content while limpets contain significant amounts of organotin compounds, ranging between 35 and 75% of the total tin. No trimethyltin was detected in green macro-algae and seawater, although limpets, fish and sediments have measurable levels.     

Differential kinetics and temperature dependence of abiotic and biotic processes controlling the environmental fate of TNT in simulated marine systems

This work seeks to understand how the balance of abiotic and biotic kinetic processes in sediments control the residual concentration of TNT in marine systems after release from ocean-dumped source. Kinetics of TNT disappearance were followed using marine sediments at different temperatures and under both biotic and presumably abiotic conditions (through sodium azide addition). Sediments exhibiting the highest rate of TNT disappearance under biotic conditions also exhibited the highest sorption affinity for TNT under abiotic conditions. Significant temperature dependence in the abiotic processes was observed in the diffusion coefficient of TNT and not sediment sorption affinity. At higher temperature, kinetics of biotic processes outpaced abiotic processes, but at low temperature, kinetics of abiotic processes were much more significant. We concluded that the differential influence of temperature on the kinetics of abiotic and biotic processes could provide distinguishing predictions for the potential residual concentration of TNT contamination in marine-sediment systems.     

The effects of sewage organic matter on biogeochemical processes within mid-shelf sediments offshore Sydney, Australia

A laboratory incubation experiment was conducted using replicate cores collected from a muddy-sand sediment facies offshore Sydney, Australia to determine what components and processes would be affected by the addition of sewage organic matter. Sewage effluent has a solid phase composition of 40% carbon (35% organic carbon), 5% nitrogen, 1% phosphorus and 5% silicate. The molecular C:N:P ratio is 92:10:1, compared to the Redfield ratio of 106:16:1 in marine phytoplankton. Sediment cores were incubated at in situ temperature in a darkened room for periods up to 95 days. Sewage organic matter was added to the cores at three different loads equivalent to 0 (T0), 65 (T1) and 130 (T2) g m⁻² of sediment. Following the addition of sewage organic matter, fluxes of oxygen (into the sediments), ammonia and phosphate (from the sediments) increased, reflecting an enhanced organic carbon supply to the sediments. Oxygen penetrated to a depth of 6 mm in the ambient cores, but the sediment oxygen content was severely depleted following the addition of the sewage-derived organic matter. Sediment porewater data, together with nutrient flux data indicate that oxygen reduction, nitrate reduction and sulphate reduction occurs within these sediments. Following the addition of sewage organic matter, increases in total nitrogen, total phosphate and total organic carbon were measured to depths of 5 cm in the sediments, suggesting that bioturbation influences nutrient and organic carbon distributions. Additionally, irrigation of the surficial sediments may play an important role in the metabolism of organic matter. These results indicate that oxygen penetration, oxygen fluxes, nitrate concentrations within porewaters, ammonia flux rates, and solid phase concentrations of total organic carbon and nutrients may be useful indicators of sediments affected by high rates of organic matter deposition onto Sydney's offshore sediments. The EPA has recently predicted maximum deposition rates of sewage particulate matter to be approximately 1 g m⁻² day⁻¹. Because of the similarities in CNP ratios of sewage organic matter and marine organic matter, the effects of sewage organic matter and marine organic matter inputs to coastal sediments may not be easily distinguishable.     

Long-term effects of crude oil on microbial processes in subarctic marine sediments: Studies on sediments amended with organic nutrients

Subarctic marine sediments amended with various organic compounds were exposed to fresh Cook Inlet crude oil at a concentration of 50 ppt for either 6 or 8 months. After the sediments were initially treated, they were returned to the approximate location where they were collected and left to be exposed to natural environmental conditions until they were retrieved for analysis. As a result of crude oil treatment, the activities of the enzymes that hydrolyse structural polysaccharides were reduced and the activities of the enzymes that hydrolyse storage polysaccharides were stimulated. In addition to these changes, we observed changes in phosphatase activity, nitrogen fixation rates, potential denitrification rates, methane concentrations, CO₂ production rates, and the glucose uptake and mineralization rates. The effect of the crude oil perturbation was different depending on the organic compound used in the amended sediments. Many of these differences could be explained by the effect of crude oil on the hydrolases which were responsible for degrading the compound in question. The results of this study suggest the effect of crude oil on microbial processes may be affected by the type of organic material present in the impacted marine sediment. This study also illustrates the value of measuring hydrolase activity in studies designed to determine the effects of this or any other pollutant on microbial processes in marine sediments.     

Mercury distribution, speciation and bioavailability in sediments from the Pearl River Estuary, Southern China

Surface sediments and sediment cores collected from the Pearl River Estuary (PRE) were analyzed for total mercury (THg) concentrations and speciation using a sequential extraction method. The mobility of Hg in sediments was also assessed using a series of single extraction methods. The surface sediments from the PRE showed slightly elevated levels of Hg, with concentrations ranging from 109 to 453 ng/g. The vertical profile of THg in sediment cores indicated an accelerated input of Hg over the past decades. The organo-chelated and strong-complexed Hg species were the dominant Hg species in the sediments, while the more mobile phases of Hg made up less than 0.5% of THg. Less than 10% of the Hg in the sediments was extracted by single extraction, depending on the extractant employed. Significant relationships were found between the total organic carbon and THg, geochemical speciation, and extractability, indicating the important role of organic matter in controlling the distribution, mobility, and bioavailability of Hg in sediments.     

Influence of the biomass content in sediment on the sediment nutrient flux for a pulsed organic load

A laboratory study was carried out to investigate the influence of the biomass content in the sediment on the rate of diagenesis of particulate organic materials (POM) and the consequent sediment oxygen demand (SOD) and nutrient fluxes. Fish food pellets were loaded into the sediment to simulate a sudden POM input. Three types of sediments with different biomass contents were tested, including a raw marine sediment, the marine sediment after one month of cultivation and an artificial sediment of sand and clay without any biomass. There was little difference in organic flux from the three different sediments. However, compared to the artificial sediment, the marine sediments had much higher SOD and ammonia flux. A mathematical model also has been developed for the SOD dynamics and nutrient fluxes. Both the experimental and simulation results indicate the important role of the biomass in the sediment in POM diagenesis, SOD and nutrient fluxes.     

Influence of the biomass content in sediment on the sediment nutrient flux for a pulsed organic load

A laboratory study was carried out to investigate the influence of the biomass content in the sediment on the rate of diagenesis of particulate organic materials (POM) and the consequent sediment oxygen demand (SOD) and nutrient fluxes. Fish food pellets were loaded into the sediment to simulate a sudden POM input. Three types of sediments with different biomass contents were tested, including a raw marine sediment, the marine sediment after one month of cultivation and an artificial sediment of sand and clay without any biomass. There was little difference in organic flux from the three different sediments. However, compared to the artificial sediment, the marine sediments had much higher SOD and ammonia flux. A mathematical model also has been developed for the SOD dynamics and nutrient fluxes. Both the experimental and simulation results indicate the important role of the biomass in the sediment in POM diagenesis, SOD and nutrient fluxes.     

Efficient trapping of organic carbon in sediments on the continental margin with high fluvial sediment input off southwestern Taiwan

Accumulation rates of marine and terrigenous organic carbon in the continental margin sediments off southwestern Taiwan were estimated from the measured concentrations and isotopic compositions of total organic carbon (TOC) and previously reported sedimentation rates. Surficial sediments were collected from the study area spanning from the narrow shelf near the Kaoping River mouth to the deep slope with depths reaching almost 3000 m. The average sediment loading of Kaoping River is 17 Mt/yr, which yields high sediment accumulation rates ranging from 0.08 to 1.44 g cm⁻² yr⁻¹ in the continental margin. About half of the discharged sediments were deposited on the margin within 120 km of the river mouth. Carbon isotopic compositions of terrestrial and marine end-members of organic matter were determined, respectively, based on suspended particulate matter (SPM) collected from three major rivers in the southwestern Taiwan and from an offshore station. All samples were analyzed for the TOC content and its isotopic composition (δ¹³C_org). The SPM samples were also analyzed for the total nitrogen (TN) content. TOC content in marine sediments ranges from 0.45% to 1.35% with the highest values on the upper slope near the Kaoping River mouth. The TOC/TN ratio of the SPM samples from the offshore station is 6.8±0.6, almost identical to the Redfield ratio, indicating their predominantly marine origin; their δ¹³C_org values are also typically marine with a mean of −21.5±0.3‰. The riverine SPM samples exhibit typical terrestrial δ¹³C_org values around −25‰. The δ¹³C_org values of surficial sediments range from −24.8‰ to −21.2‰, showing a distribution pattern influenced by inputs from the Kaoping River. The relative contributions from marine and terrestrial sources to sedimentary organic carbon were determined by the isotope mixing model with end-member compositions derived from the riverine and marine SPM. High fluvial sediment inputs lead to efficient trapping of organic carbon over a wide range of water depth in this continental margin. The marine organic accumulation rate ranges from 1.6 to 70 g C m⁻² yr⁻¹ with an area weighted mean of 4.2 g C m⁻² yr⁻¹, which is on a par with the mean terrestrial contribution and accounts for 2.3% of mean primary production. The depth-dependent accumulation rate of marine organic carbon can be simulated with a function involving primary productivity and mineral accumulation rate, which may be applicable to other continental margins with high sedimentation rates. Away from the nearshore area, the content of terrigenous organic carbon in surficial sediments decreases with distance from the river mouth, indicating its degradation in marine environments.     

Distribution and sources of polynuclear aromatic hydrocarbons in Mangrove surficial sediments of Deep Bay, China

Twelve sediment samples collected from three transects of mangrove swamp of Deep Bay, Shenzhen, China, were determined for polynuclear aromatic hydrocarbons (PAHs). The total PAHs concentrations ranged from 237 to 726 ng g(-1) dry weight, and showed strong correlation with total organic carbon (TOC), clay content and Pb concentrations. The highest PAHs concentrations were found in the samples from mangrove sediments. Overall, PAHs in Deep Bay sediment were lower than those in other developed areas. The biological effect due to PAHs alone in Deep Bay is expected to be low, based on the comparisons of individual and total PAHs concentrations determined in the sediment with those in USEPA sediment quality guidelines. Four and five-ring compounds dominated the PAHs composition pattern profiles. Principal component analysis (PCA) was applied to further investigate the source of PAHs. The PAH sources of Deep Bay mangrove swamp were suggested to be primarily combustion of fossil fuel, especially leaded-gasoline exhaust.     

In situ oxygen uptake rates by coastal sediments under the influence of the Rhône River (NW Mediterranean Sea)

The influence of riverine inputs on biogeochemical cycling and organic matter recycling in sediments on the continental shelf off the Rhône River mouth (NW Mediterranean Sea) was investigated by measuring sediment oxygen uptake rates using a combination of in situ and laboratory techniques. Four stations were investigated during two cruises in June 2001 and June 2002, with depths ranging from 9 to 192 m and over a distance to the Rhône River mouth ranging from 4 to 36 km. Diffusive oxygen uptake (DOU) rates were determined using an in situ sediment microprofiler and total oxygen uptake (TOU) rates were measured using sediment core incubations. There was good agreement between these two techniques which indicates that the non-diffusive fraction of the oxygen flux was minimal at the investigated stations. DOU rates ranged from 3.7±0.4 mmol O₂ m⁻² d⁻¹ at the continental shelf break to 19.3±0.5 mmol O₂ m⁻² d⁻¹ in front of the Rhône River mouth. Sediment oxygen uptake rates mostly decreased with increasing depth and with distance from the Rhône mouth. The highest oxygen uptake rate was observed at 63 m on the Rhône prodelta, corresponding to intense remineralization of organic matter. This oxygen uptake rate was much larger than expected for the increasing bathymetry, which indicates that biogeochemical cycles and benthic deposition are largely influenced by the Rhône River inputs. This functioning was also supported by the detailed spatial distribution of total organic carbon (TOC), total nitrogen (TN) and C/N atomic ratio in surficial sediments. Sediments of the Rhône prodelta are enriched in organic carbon (2–2.2%) relative to the continental shelf sediments (<1%) and showed C/N ratios exceeding Redfield stoichiometry for fresh marine organic matter. A positive exponential correlation was found between DOU and TOC contents (r²=0.98, n=4). South-westward of the Rhône River mouth, sediments contained highly degraded organic matter of both terrestrial and marine origin, due to direct inputs from the Rhône River, sedimentation of marine organic matter and organic material redeposition after resuspension events.     

Degradation rates of low molecular weight PAH correlate with sediment TOC in marine subtidal sediments

The degradation rate of low molecular weight (LMW) polycyclic aromatic hydrocarbons (PAH) in subtidal marine sediments was found to correlate with sediment total organic carbon (TOC) in stations sampled two or more times after the North Cape No. 2 fuel oil spill. With 2.5-5 months between samplings, stations with lower sediment TOC had lower fractions of LMW PAH remaining at the time of the second sampling. Apparent first-order degradation rate constants calculated for each station varied by nearly an order of magnitude between stations with a range of TOC from 0.4% to 7.3%. The correlation of degradation rate with sediment TOC can be used to provide improved and site-specific predictions of the initial time-course of LMW PAH concentrations in sediments after oil spills.     

Levels of estrogenic compounds in Xiamen Bay sediment, China

Concentrations of seven estrogenic compounds, i.e., estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol(EE2), diethylstilbestrol (DES), nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA), were determined in sediments and pore water from Xiamen Bay in China, and their distributions and potential risks in the Bay were assessed. Total estrogenic compounds concentrations varied from 49.20 to 1230.69 ng/g dw in sediments and from 102.33 to 4376.60 ng/L in pore water. The highest levels of these compounds were found at Yundang Lagoon. The results showed that estrogenic compounds in Xiamen Bay originated mainly from municipal wastewaters. Compared with other areas, Xiamen Bay was contaminated with high levels of estrogen hormones. This contamination poses a potential threat to benthic organisms. Although a good relationship (r = 0.94) was observed between the estrogenic compounds concentrations and total organic carbon (TOC) contents in sediments, which did not indicate that the sediment organic matter favors the accumulation of the detected estrogenic compounds.     

Abbau von nitroaromatischen Xenobiotika durch Ozonisierung und biologische Nachbehandlung

Degradation of Nitroaromatic Xenobiotics by Ozonization and Subsequent Biological Treatment Ozonization for 2,4-dinitrotoluene (DNT) and 4-nitroaniline (NA) was conducted in completely mixed reactors by semi-batch tests. At pH 7, both direct and radical reactions contribute to the oxidation of the nitroaromatic compounds. In the dominantly mass transfer-limited reaction, a specific ozone absorption of A* = 3.0…3.5 g g^?1 was measured for a ?98% elimination of the target compounds. About 80…90% of the input ozone were absorbed, and 10…20% left the system unreacted. At pH 7, the degree of DOC reduction increased linearly with the specific ozone absorption to final values of 35% (NA) and 44% (DNT), respectively. A subsequent biological treatment of the oxidation products by non-acclimated bacteria increased the degree of mineralization to 75%. Compared to ozonization alone, 35 and 50% of ozone were thus saved by the sequential chemical-biological process. Batch tests with a real wastewater from the alkaline hydrolysis of a mixture of 2,4,6-trinitrotoluene (TNT) and 1,3-dinitrobenzene (DNB) confirmed the approach. No reduction in the required ozone dosage was achieved in a completely mixed continuous system of ozonization followed by biodegradation even when compared to batch ozonization alone. Therefore, the reduction of longitudinal mixing in continuous ozonization systems is regarded to be of fundamental importance.     

Risks posed by trace organic contaminants in coastal sediments in the Pearl River Delta, China

Local marine environments in China's Pearl River Delta (PRD), the most rapidly developing region in one of the world's fastest growing economies, have been experiencing significant environmental stress during the past decades. This investigation was conducted to determine the status and trends of persistence organic pollutants (POPs) such as polycyclic aromatic hydrocarbons (PAHs), petroleum hydrocarbons (PHCs), polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and dioxin-related compounds in marine sediments collected from sixteen coastal stations in the Pearl River Delta (PRD) in March 2003. Elevated concentrations of PAHs (94-4300 ng/g), PCBs (6.0-290 ng/g), PHCs (14-150 microg/g), and DDTs (1.4-600 ng/g) were detected in sediment samples. In addition, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-like activities in the sediment samples were estimated to range from 0.3 to 440 pg TCDD-EQ/g. Sediments collected from Xiashan contained the greatest concentrations of trace organic contaminations amongst all the sampling stations in the present study. The degree of trace organic contamination was, in general, more severe at stations situated along the west shores of the PRD than their counterparts in the east. A preliminary assessment was performed to examine the probable risks to the marine ecosystem due to POPs. The results showed that OC pesticide contamination in the PRD was particularly serious and might pose a threat to the health of the marine inhabitants.     

Clostridium perfringens as a potential indicator for the presence of sewage solids in marine sediments

Marine sediment cores collected from several depths of water and distances from a California sewage outfall were tested to see if sediments influenced by sewage solids were a reservoir of enteric pathogens, and if concentrations of indicator bacteria were related to the presence of sewage solids. Vertical distributions of microorganisms in marine sediments were determined; there was a decrease of indicator bacteria with increasing sediment depth. Aeromonas was randomly isolated, but none of the enteric bacterial pathogens or viruses were detected. While classic indicator bacteria were of little value in predicting the presence of pathogens, or relative amounts of sewage solids, Clostridium perfringens may be a suitable indicator. Clostridium perfringens concentrations were not related to the presence of pathogens in sediments.     

Distribution and enrichment evaluation of heavy metals in Mejillones Bay (23°S), Northern Chile: Geochemical and statistical approach

A suite of 36 surface sediment samples, taken between 10 and 100 m water depth in Mejillones Bay (Northern Chile), were analyzed for mineralogy, grain size, total organic carbon, Al, and heavy metal content (Cd, Zn, Ni, Mn, V, Mo). Quartz and feldspars were the main lithogenic minerals and carbonate the predominant biogenic mineral. Sediments were fine sands in the shallow zone and organic silt in the deeper zone.

Enrichment Factor and Factor Analysis approach showed that the presence of Mn in the marine sediment of Mejillones is due to a partial influence of continental input, while all other metals are not supported by lithogenic debris. Although all metals showed high concentrations in the marine sediment of Mejillones Bay, comparison between metal concentration in surface sediments and preindustrial levels in this bay, show that present values agree with natural levels.     

Aliphatic and polyaromatic hydrocarbons in bottom sediments of offshore mouth area of the Volga

Data on the concentration and composition of aliphatic and polyaromatic hydrocarbons in the surface layer and the body of bottom sediments in Volga delta and on the northern Caspian shelf are given. Volga delta sediments are shown to contain large concentrations of organic compounds. It is established that the concentrations of organic compounds is largely dependent on the dispersiveness of sediments. Anthropogenic hydrocarbons, both oil and pyrogenic, fail to pass the marginal filter of the Volga River and do not reach the open part of the sea. Therefore, the hydrocarbons contained in the bottom sediments on the Caspian Sea shelf are mostly of natural genesis. The distribution of organic compounds in the bottom sediment strata has a complex character. In some cases, their concentration increases because of the higher flux of hydrocarbons (especially, polyarenes in the 1950s).