Assessment of phthalic acid esters plasticizers in sediments of coastal Alabama, USA: Occurrence, source, and ecological risk.

Considering the ubiquitous occurrences and ecotoxicity of phthalates (PAEs), it is essential to understand their sources, distribution, and associated ecological risks of PAEs in sediments to assess the environmental health of estuaries and support effective management practices. This study provides the first comprehensive dataset on the occurrence, spatial variation, inventory, and potential ecological risk assessment of PAEs in surface sediments of commercially and ecologically significant estuaries in the southeastern United States, Mobile Bay and adjoining eastern Mississippi Sound. Fifteen PAEs were widely detected in the sediments of the study region, with total concentrations varying between 0.02 and 3.37 µg/g. The dominance of low-molecular-weight (LMW) PAEs (DEP, DBP and DiBP) relative to high-molecular-weight (HMW) PAEs (DEHP, DOP, DNP) indicates that residential activities have stronger impacts than industrial activities on PAE distributions. The total PAE concentrations displayed an overall decreasing trend with increasing bottom water salinity, with the maximum concentrations occurring near river mouths. These observations suggest that river inputs were an important pathway by which PAEs were transported to the estuary. Linear regression models identified sediment adsorption (measured by total organic carbon and median grain size) and riverine inputs (measured by bottom water salinity) as significant predictors for the concentrations of LMW and HMW PAEs. Estimated 5-year total inventories of sedimentary PAEs in Mobile Bay and the eastern Mississippi Sound were 13.82 tons and 1.16 tons, respectively. Risk assessment calculations suggest that LMW PAEs posed a medium-to-high risk to sensitive aquatic organisms, and DEHP posed a low or negligible risk to the aquatic organisms. The results of this study provide important information needed for establishing and implementing effective practices for monitoring and regulating plasticizer pollutants in estuaries.

Sources and composition of natural and anthropogenic hydrocarbons in sediments from an impacted estuary.

Hydrocarbons in estuarine sediments provide information on sources of sedimentary organic matter (OM), and they are thus useful for tracing natural and anthropogenic OM inputs to the estuary. Here, we assessed the amounts, compositions and sources of natural and anthropogenic hydrocarbons from the sediments of a large, ecologically important estuary, Mobile Bay in Southeast USA. TOC/TN ratios and δ13C of organic carbon suggest that the bulk natural OM was sourced from marine phytoplankton and bacteria mixed with marsh and terrigenous C3 plants. Normal alkanes show high proportions of long-chain compounds with a high Carbon Preference Index, indicating the importance of C3 plants-derived OM in Mobile Bay. High concentrations of biogenic hopanes and perylene indicate microbial sources and degradation played an important role in shaping OM compositions. Anthropogenic hydrocarbons, αß-hopanes and polycyclic aromatic hydrocarbons (PAHs), were widely detected in Mobile Bay sediments. The source diagnostic ratios of hopanes and steranes suggest they were sourced from coal and diesel combustions. The source diagnostic ratios of PAHs, together with a positive correlation between PAHs and total mercury, suggests that PAHs originated primarily from coal combustion. We proposed two ratios, αß-hopanes/(ßß-hopanes+hopenes) and 16 PAHs/perylene, to evaluate anthropogenic versus natural contributions of hydrocarbons. These ratios were higher in the western estuary than in the eastern estuary, suggesting elevated anthropogenic hydrocarbon inputs to the western estuary. Correspondingly, the toxic equivalent quantity (TEQBaQ) of PAHs showed a higher ecological risk for the western estuary. This spatially uneven distribution of hydrocarbon pollutants can be attributed to more concentrated urban and industrial areas on the western shore, suggesting the importance of adjacent pollution sources. Collectively, our results provide new insights into the origins and dynamics of natural and anthropogenic OM and highlight the significance of coal combustion in contributing hydrocarbon pollutants in Mobile Bay sediments.

Quantifying colloid fate and transport through dense vegetation and soil systems using a particle-plugging tempered fractional-derivative model.

Colloid contaminants are widely distributed in surface runoff from crop land and can be effectively removed by vegetative filter strips (VFS), whose quantification however proves difficult. Standard mechanism-based models contain many unknown parameters with intrinsic uncertainty, limiting their applicability and potential extension for other environmental conditions and colloid contaminant types. To remedy this limitation and capture the complex dynamics of colloids through the soil-vegetation system, this study proposes a parsimonious, particle-plugging tempered fractional advection-dispersion eq. (P-TFADE) with a few empirical parameters, which is built upon the promising fractional calculus engine. The P-TFADE model extends the promising tempered fractional derivative model by incorporating a plugging term, which is then proved to be able to capture both the plugging dynamics and tailing behavior of colloids under various hydrologic and geochemical conditions. Applications also show that the two critical parameters in the P-TFADE model, the time index (α) and plugging coefficient (Kp), can efficiently characterize the impact of the flowrate and ionic condition on transport of different sized colloids observed in our laboratory. In addition, the vegetation type determines the overall structure of the soil-vegetation system, whose impact on the colloid removal efficiency can be quantified by adding a parameter λ in the physical model. Therefore, the novel P-TFADE model can reduce the model uncertainty and help us further understand the nature of colloid dynamics through dense vegetation and soil systems.

Bacterial community shift in the coastal Gulf of Mexico salt-marsh sediment microcosm in vitro following exposure to the Mississippi Canyon Block 252 oil (MC252).

In this study, we examined the responses by the indigenous bacterial communities in salt-marsh sediment microcosms in vitro following treatment with Mississippi Canyon Block 252 oil (MC252). Microcosms were constructed of sediment and seawater collected from Bayou La Batre located in coastal Alabama on the Gulf of Mexico. We used an amplicon pyrosequencing approach on microcosm sediment metagenome targeting the V3-V5 region of the 16S rRNA gene. Overall, we identified a shift in the bacterial community in three distinct groups. The first group was the early responders (orders Pseudomonadales and Oceanospirillales within class Gammaproteobacteria), which increased their relative abundance within 2 weeks and were maintained 3 weeks after oil treatment. The second group was identified as early, but transient responders (order Rhodobacterales within class Alphaproteobacteria; class Epsilonproteobacteria), which increased their population by 2 weeks, but returned to the basal level 3 weeks after oil treatment. The third group was the late responders (order Clostridiales within phylum Firmicutes; order Methylococcales within class Gammaproteobacteria; and phylum Tenericutes), which only increased 3 weeks after oil treatment. Furthermore, we identified oil-sensitive bacterial taxa (order Chromatiales within class Gammaproteobacteria; order Syntrophobacterales within class Deltaproteobacteria), which decreased in their population after 2 weeks of oil treatment. Detection of alkane (alkB), catechol (C2,3DO) and biphenyl (bph) biodegradation genes by PCR, particularly in oil-treated sediment metacommunity DNA, delineates proliferation of  the hydrocarbon degrading bacterial community. Overall, the indigenous bacterial communities in our salt-marsh sediment in vitro microcosm study responded rapidly and shifted towards members of the taxonomic groups that are capable of surviving in an MC252 oil-contaminated environment.

Attenuation of trace elements in coal fly ash leachates by surfactant-modified zeolite.

Potential leaching of trace elements from older, unlined fly ash disposal facilities is a serious threat to groundwater and surface water contamination. Therefore, effective methods for containing the pollutant elements within the unlined coal combustion products (CCPs) disposal facilities are required to minimize any potential impact of leachate emanating from such facilities into the nearby environment. Because surfactant-modified zeolite (SMZ) has the potential to sequester both cationic and anionic trace elements from aqueous solutions, bench-scale batch and column experiments were performed to test its ability to remediate trace elements in leachates generated from both alkaline and acidic fly ash samples. Fly ash leachate treatment results showed the potential application of SMZ as an effective permeable reactive barrier (PRB) material to control the dispersion of heavy metals and metalloids from ash disposal sites. Quantitative comparison of the elemental composition of SMZ-treated and untreated leachates indicated that SMZ was effective in decreasing the concentrations of trace elements in fly ash leachates. Similarly, SMZ treatment column experiments showed the delayed peak leaching events and overall reductions in leachate concentrations of trace elements. The effectiveness of SMZ column treatments, however, decreased with time potentially due to the saturation of sorption sites.

Modeling arsenic sorption in the subsurface with a dual-site model.

Arsenic is a well-known groundwater contaminant that causes toxicological and carcinogenic effects in humans. Predicting the transport of arsenic in the subsurface is often problematic because of its complex sorption characteristics. Numerous researchers have reported that arsenic sorption on soil material is initially fast and then subsequently slow. A dual-site numerical sorption model was previously developed to describe arsenic desorption from arsenic-contaminated soils in batch experiments in terms of two different release mechanisms. Experiments involving synthetic acid rain leaching of four arsenic-contaminated soil columns were performed to verify the dual-site numerical sorption model in the context of one-dimensional vertical transport. The fitted models successfully simulated the signature long tailings and the two-stage arsenic leaching patterns for all four soil columns. The dual-site sorption model was incorporated within the general solute transport simulation code Modular Three-Dimensional Multispecies (MT3DMS), version 5.10. The resulting version was named MT3DDS and is available for public access. This experimental study has shown that MT3DDS is capable of simulating phase redistribution during transport, and thus provides a new numerical tool for simulating arsenic transport in the subsurface.

Modeling arsenic desorption from herbicide-contaminated soils.

The application of arsenical herbicides has created legacy environmental problems by contaminating soil in some agricultural areas and at various industrial sites. Numerous previous studies have suggested that the adsorption of arsenic by common soil components is largely controlled by kinetic factors. Four arsenic-contaminated soil samples collected from industrial sites were characterized and subjected to sequential leaching using a synthetic acid rain solution in order to study the release of arsenic. A dual-site numerical sorption-desorption model was constructed that describes arsenic desorption from these soils in terms of two different release mechanisms: Release from type I (equilibrium) and type II (kinetic) sorption sites. Arsenic held on both type I and II sorption sites is accessible through extensive acid rain leaching. Arsenic desorption from these sites follows a linear Kd model; the manner of approaching the Kd model, however, differs. Arsenic desorption from type I sites reached equilibrium with the aqueous phase under the physical environment provided by the experiment (shaking for 24 h at 25 degrees C), while desorption from type II sites followed a first-order kinetic pattern when approaching equilibrium. During synthetic acid rain sequential leaching of the soils, type I sites released their sorbed arsenic rapidly and subsequent desorption was dominated by the kinetic release of arsenic from type II sites. This shift in desorption mechanism dominance generated data corresponding to two intersecting straight lines in the n-logC dimension for all four soils. The dual-site desorption model was solved analytically and proven to be successful in simulating sorption processes where two different mechanisms are simultaneously controlling the aqueous concentration of a trace element.

The environmental fate of arsenic in surface soil contaminated by historical herbicide application.

Soils from many industrial sites are contaminated with arsenic because of the historical application of herbicide containing arsenic trioxide. The strong affinity of aqueous arsenic species for soil components has led to the retention of significant amounts of arsenic in surface soils decades after the original source application. Soil collected from a site which received a one-time surficial application of arsenical herbicide in the 1950s was investigated to understand the fate of arsenic under natural leaching conditions. Sequential chemical extraction of the contaminated soil revealed that the majority of the arsenic is in its secondary form. The synthetic acid rain leaching of arsenic from the weathered soil can be divided into two distinct stages. During the first stage, the leachate arsenic concentration underwent a rapid decline which suggests an equilibrium-controlled release event. The second leaching stage was marked by a slow, steady release of arsenic, a signature of a kinetically controlled process. A mathematical approach was employed to identify and describe the two distinct arsenic releasing processes (equilibrium desorption and kinetic desorption). This model considers both desorption processes simultaneously and produces leachate arsenic concentrations in good agreement with the measured data. According to the modeling results, 20% of the arsenic remaining in the soil resides in the herbicide source material after five decades of natural leaching; 25% exists on reversible adsorption sites and 55% is present on irreversible adsorption sites.

In situ chemical fixation of arsenic-contaminated soils: an experimental study.

This paper reports the results of an experimental study testing a low-cost in situ chemical fixation method designed to reclaim arsenic-contaminated subsurface soils. Subsurface soils from several industrial sites in southeastern U.S. were contaminated with arsenic through heavy application of herbicide containing arsenic trioxide. The mean concentrations of environmentally available arsenic in soils collected from the two study sites, FW and BH, are 325 mg/kg and 900 mg/kg, respectively. The soils are sandy loams with varying mineralogical and organic contents. The previous study [Yang L, Donahoe RJ. The form, distribution and mobility of arsenic in soils contaminated by arsenic trioxide, at sites in Southeast USA. Appl Geochem 2007;22:320-341] indicated that a large portion of the arsenic in both soils is associated with amorphous aluminum and iron oxyhydroxides and shows very slow release against leaching by synthetic precipitation. The soil's amorphous aluminum and iron oxyhydroxides content was found to have the most significant effect on its ability to retain arsenic. Based on this observation, contaminated soils were reacted with different treatment solutions in an effort to promote the formation of insoluble arsenic-bearing phases and thereby decrease the leachability of arsenic. Ferrous sulfate, potassium permanganate and calcium carbonate were used as the reagents for the chemical fixation solutions evaluated in three sets of batch experiments: (1) FeSO(4); (2) FeSO(4) and KMnO(4); (3) FeSO(4), KMnO(4) and CaCO(3). The optimum treatment solutions for each soil were identified based on the mobility of arsenic during sequential leaching of treated and untreated soils using the fluids described in EPA Method 1311 [USEPA. Method 1311: toxicity characteristic leaching procedure. Test methods for evaluating solid waste, physical/chemical methods. 3rd ed. Washington, DC: U.S. Environmental Protection Agency, Office of Solid Waste. U.S. Government Printing Office; 1992] toxic characteristics leaching procedure (TCLP) and EPA Method 1312 [USEPA. Method 1312: synthetic precipitation leaching procedure. Test methods for evaluating solid waste, physical/chemical methods. 3rd ed. Washington, DC: U.S. Environmental Protection Agency, Office of Solid Waste. U.S. Government Printing Office; 1994] synthetic precipitation leaching procedure (SPLP). Both FW and BH soils showed significant decreases in arsenic leachability for all three treatment solutions, compared to untreated soil. While soils treated with solution (3) showed the best results with subsequent TCLP sequential leaching, SPLP sequential leaching of treated soils indicated that lowest arsenic mobility was obtained using treatment solution (1). Treatment solution (1) with only FeSO(4) is considered the best choice for remediation of arsenic-contaminated soil because SPLP sequential leaching better simulates natural weathering. Analysis of treated soils produced no evidence of newly-formed arsenic-bearing phases in either soil after treatment. Sequential chemical extractions of treated soils indicate that surface complexation of arsenic on ferric hydroxide is the major mechanism for the fixation process.