Sorption characteristics of a nonionic surfactant during remediation of contaminated soil with different organic content

Surfactant enhanced subsurface remediation has gained importance in soil remediation. Since surfactants can be sorbed on soils, the concentration of free surfactant could drop below the critical micelle concentration, CMC, which may reduce the ability of the surfactant to solubilize the contaminants in soils. ^ The main goal of this research was to study the factors affecting the surfactant sorption on soil such as surfactant concentration, soil organic content, and organic contaminants in soil and to determine the organic contaminants removed from soils by surfactant. The results would be served as the basis for the implementation of a future study in the pilot scale and field scale for surfactant enhanced subsurface remediation. ^ This research study investigated the relationship between the organic content of soils and the sorption characteristics of a nonionic surfactant, Triton X-100. The experiments were performed using uncontaminated soils and soil contaminated with naphthalene and decane. The first part of the experiments were conducted in batch mode utilizing surface tension technique to determine the CMC of surfactant Triton X-100 and the effective CMC in the soil/aqueous system. The sorption of Triton X-100 was calculated from the surface tension measurements. The second part of the experiments utilized the SPME/GC/FID technique to determine the concentration of the contaminants solubilized from the soils by the surfactant Triton X-100 at different concentrations. ^ The results indicated that when the concentration of surfactant was lower than the CMC, the amount of surfactant sorbed on soil increased with the increasing surfactant concentration and the surfactant sorption characteristics of the uncontaminated soils could be modeled by the Freundlich isotherm. For the contaminated soils, the amount of surfactant sorbed was higher than those for the uncontaminated soils. The amount of surfactant sorbed on soils also depends on the organic content in the soils. The higher the organic content in the soil, higher is the amount of surfactant sorbed onto the soil. When the concentration of surfactant was higher than the CMC, the amount of surfactant added into the soil/aqueous system will increase the number of micelle and it increase the solubilization of organic contaminant from the soils. The ratio of the moles of organic contaminant solubilized to the moles of surfactant present as micelles is called the molar solubilization ratio (MSR). MSR value for naphthalene was about 0.16 for the soil-water systems. The organic content of soil did not appear to affect MSR for naphthalene. On the other hand, the MSR values for decane were 0.52, 0.39 and 0.38 for soils with 25%, 50% and 75% organic content, respectively. ^

Natural organic matter and colloid-facilitated arsenic transport and transformation in porous soil media

Prediction of arsenic transport and transformation in soil environment requires understanding the transport mechanisms and proper estimation of arsenic partitioning tong all three phases in soil/aquifer systems: mobile colloids, mobile soil solution, and immobile soil solids. The primary purpose of this research is to study natural dissolved organic matter (DOM)/colloid-facilitated transport of arsenic and understand the role of soil derived carriers in the transport and transformation of both inorganic and organoarsenicals in soils. ^ DOM/colloid facilitated arsenic transport and transformation in porous soil media were investigated using a set of experimental approaches including batch experiment, equilibrium membrane dialysis experiment and column experiment. Soil batch experiment was applied to investigate arsenic adsorption on a variety of soils with different characteristics; Equilibrium membrane dialysis was employed to determine the 'free' and 'colloid-bound/complexed' arsenic in water extracts of chosen soils; Column experiments were also set up in the laboratory to simulate arsenic transport and transformation through golf course soils in the presence and absence of soil-derived dissolved substances. ^ The experimental results revealed that organic matter amendments effectively reduced soil arsenic adsorption. The majority of arsenic present in the soil extracts was associated with small substances of molecular weight (MW) between 500 and 3,500 Da, Only a small fraction of arsenic was associated with higher MW substances (MW > 3,500 Da), which was operationally defined as colloidal part in this study. The association of arsenic and DOM in the soil extracts strongly affected arsenic bioavailability, arsenic transport and transformation in soils. The results of column experiments revealed arsenic complicated behavior with various processes occurring in soils studied, including: soil arsenic' adsorption, facilitated arsenic transportation by dissolved substances presented in soil extracts and microorganisms involved arsenic species transformation. ^ Soil organic matter amendments effectively reduce soil arsenic adsorption capability either by scavenging 'soil arsenic adsorption sites or by interactions between arsenic species and dissolved organic chemicals in soil solution. Close attention must be paid for facilitated arsenic transport by dissolved substances presented in soil solution and microorganisms involved arsenic species transformation in arsenic-contaminated soils.^

Experimental analysis of soil and dust stabilizers for controlling displacement of contaminated soils by wind tunnel experiments

During the remediation of burial grounds at the US Department of Energy's (DOE's) Hanford Site in Washington State, the dispersion of contaminated soil particles and dust is an issue that is faced by site workers on a daily basis. This contamination problem is even more of a concern when one takes into account the semi-arid characteristics of the region where the site is located. To mitigate this problem, workers at the site use a variety of engineered methods to minimize the dispersion of contaminated soil and dust (i.e. use of water and/or suppression agents that stabilizes the soil prior to soil excavation, segregation, and removal activities). A primary contributor to the dispersion of contaminated soil and dust is wind soil erosion. The erosion process occurs when the wind speed exceeds a certain threshold value which depends on a number of factors including wind force loading, particle size, surface soil moisture, and the geometry of the soil. Thus under these circumstances, the mobility of contaminated soil and generation and dispersion of particulate matter are significantly influenced by these parameters. This dependence of soil and dust movement on threshold shear velocity, fixative dilution and/or application rates, soil moisture content, and soil geometry were studied for Hanford's sandy soil through a series of wind tunnel experiments, laboratory experiments and theoretical analysis. In addition, the behavior of plutonium (Pu) powder contamination in the soil was studied by introducing a Pu simulant (cerium oxide). The results showed that soil dispersion and PM10 concentrations decreased with increasing soil moisture. Also, it was shown that the mobility of the soil was affected by increasing wind velocity. It was demonstrated that the use of fixative products greatly decreased the amount of soil and PM10 concentrations when exposed to varying wind conditions. In addition, it was shown that geometry of the soil sample affected the velocity profile and calculation of roughness surface coefficient when comparing round and flat soil samples. Finally, threshold shear velocities were calculated for soil with flat surface and their dependency on surface soil moisture was demonstrated. A theoretical framework was developed to explain these dependencies.

Evaluating the relative contributions of hydroperiod and soil fertility on growth of south Florida mangroves

Low and high water periods create contrasting challenges for trees inhabiting periodically flooded wetlands. Low to moderate flood durations and frequencies may bring nutrient subsidies, while greater hydroperiods can be energetically stressful because of oxygen deficiency. We tested the hypothesis that hydroperiod affects the growth of mangrove seedlings and saplings in a greenhouse experiment by varying flood duration while keeping salinity and soil fertility constant. We measured the growth of mangrove trees along a hydroperiod gradient over a two-year period by tracking fine-scale diameter increment. Greenhouse growth studies indicated that under a full range of annual flood durations (0–8760 h/year), hydroperiod alone exerted a significant influence on growth for one species, Laguncularia racemosa, when flooding was imposed for two growing seasons. Field evaluations, on the other hand, indicated that increased flood duration may provide nutrient subsidies for tree growth. Diameter growth was related curvilinearly to site hydroperiod, including flood duration and frequency, as well as to salinity and soil fertility. An analysis of soil physico-chemical parameters suggests that phosphorus fertility, which was also linked directly to hydroperiod, is likely to influence growth on south Florida mangrove sites. The physical removal of phosphorus by greater flood frequencies from upland sources and/or addition of phosphorus from tidal flooding balanced against increased soil aeration and reduced water deficits may be an extremely important growth determinant for south Florida mangroves.

Sediment and soil organic matter source assessment as revealed by the molecular distribution and carbon isotopic composition of n-alkanes

The assessment of organic matter (OM) sources in sediments and soils is a key to better understand the biogeochemical cycling of carbon in aquatic environments. While traditional molecular marker-based methods have provided such information for typical two end member (allochthonous/terrestrial vs. autochthonous/microbial)-dominated systems, more detailed, biomass-specific assessments are needed for ecosystems with complex OM inputs such as tropical and sub-tropical wetlands and estuaries where aquatic macrophytes and macroalgae may play an important role as OM sources. The aim of this study was to assess the utility of a combined approach using compound specific stable carbon isotope analysis and an n-alkane based proxy (Paq) to differentiate submerged and emergent/terrestrial vegetation OM inputs to soils/sediments from a sub-tropical wetland and estuarine system, the Florida Coastal Everglades. Results show that Paq values (0.13–0.51) for the emergent/terrestrial plants were generally lower than those for freshwater/marine submerged vegetation (0.45–1.00) and that compound specific δ13C values for the n-alkanes (C23 to C31) were distinctively different for terrestrial/emergent and freshwater/marine submerged plants. While crossplots of the Paq and n-alkane stable isotope values for the C23n-alkane suggest that OM inputs are controlled by vegetation changes along the freshwater to marine transect, further resolution regarding OM input changes along this landscape was obtained through principal component analysis (PCA), successfully grouping the study sites according to the OM source strengths. The data show the potential for this n-alkane based multi-proxy approach as a means of assessing OM inputs to complex ecosystems.

Using soil profiles of seeds and molecular markers as proxies for sawgrass and wet prairie slough vegetation in Shark Slough, Everglades National Park

We measured the abundance of Cladium jamaicense (Crantz) seeds and three biomarkers in freshwater marsh soils in Shark River Slough (SRS), Everglades National Park (ENP) to determine the degree to which these paleoecological proxies reflect spatial and temporal variation in vegetation. We found that C. jamaicense seeds and the biomarkers Paq, total lignin phenols (TLP) and kaurenes analyzed from surface soils were all significantly correlated with extant aboveground C. jamaicense biomass quantified along a vegetation gradient from a C. jamaicense to a wet prairie/slough (WPS) community. Our results also suggest that these individual proxies may reflect vegetation over different spatial scales: Paq and kaurenes correlated most strongly (R 2 = 0.88 and 0.99, respectively) with vegetation within 1 m of a soil sample, while seeds and TLP reflected vegetation 0–20 m upstream of soil samples. These differences in the spatial scale depicted by the different proxies may be complementary in understanding aspects of historic landscape patterning. Soil profiles of short (25 cm) cores showed that downcore variation in C. jamaicense seeds was highly correlated with two of the three biomarkers (Paq, R 2 = 0.84, p<0.005; TLP, R 2 = 0.97, p<0.0001), and all four of the proxies indicated a recent increase in C. jamaicense biomass at the site. Using a preliminary depth-to-age relationship based on matching charcoal peaks with available ENP fire records (1980-present) specific to our coring site, we found that peak-depths in C. jamaicense seed concentration appeared to correspond to recent minimum water levels (e.g., 1989 and 2001), and low seed abundance corresponded to high water levels (e.g., 1995), consistent with the known autecology of C. jamaicense. In summary, the combination of C. jamaicense seeds and biomarkers may be useful for paleoecological reconstruction of vegetation change and ultimately in guaging the success of ongoing efforts to restore historic hydrologic conditions in the South Florida Everglades.

Hurricane Wilma’s impact on overall soil elevation and zones within the soil profile in a mangrove forest

Soil elevation affects tidal inundation period, inundation frequency, and overall hydroperiod, all of which are important ecological factors affecting species recruitment, composition, and survival in wetlands. Hurricanes can dramatically affect a site’s soil elevation. We assessed the impact of Hurricane Wilma (2005) on soil elevation at a mangrove forest location along the Shark River in Everglades National Park, Florida, USA. Using multiple depth surface elevation tables (SETs) and marker horizons we measured soil accretion, erosion, and soil elevation. We partitioned the effect of Hurricane Wilma’s storm deposit into four constituent soil zones: surface (accretion) zone, shallow zone (0–0.35 m), middle zone (0.35–4 m), and deep zone (4–6 m). We report expansion and contraction of each soil zone. Hurricane Wilma deposited 37.0 (±3.0 SE) mm of material; however, the absolute soil elevation change was + 42.8 mm due to expansion in the shallow soil zone. One year post-hurricane, the soil profile had lost 10.0 mm in soil elevation, with 8.5 mm of the loss due to erosion. The remaining soil elevation loss was due to compaction from shallow subsidence. We found prolific growth of new fine rootlets (209 ± 34 SE g m−2) in the storm deposited material suggesting that deposits may become more stable in the near future (i.e., erosion rate will decrease). Surficial erosion and belowground processes both played an important role in determining the overall soil elevation. Expansion and contraction in the shallow soil zone may be due to hydrology, and in the middle and bottom soil zones due to shallow subsidence. Findings thus far indicate that soil elevation has made substantial gains compared to site specific relative sea-level rise, but data trends suggest that belowground processes, which differ by soil zone, may come to dominate the long term ecological impact of storm deposit.

Patterns of Soil Bacteria and Canopy Community Structure Related to Tropical Peatland Development

Natural environmental gradients provide important information about the ecological constraints on plant and microbial community structure. In a tropical peatland of Panama, we investigated community structure (forest canopy and soil bacteria) and microbial community function (soil enzyme activities and respiration) along an ecosystem development gradient that coincided with a natural P gradient. Highly structured plant and bacterial communities that correlated with gradients in phosphorus status and soil organic matter content characterized the peatland. A secondary gradient in soil porewater NH4 described significant variance in soil microbial respiration and β-1-4-glucosidase activity. Covariation of canopy and soil bacteria taxa contributed to a better understanding of ecological classifications for biotic communities with applicability for tropical peatland ecosystems of Central America. Moreover, plants and soils, linked primarily through increasing P deficiency, influenced strong patterning of plant and bacterial community structure related to the development of this tropical peatland ecosystem.

Multiplex PCR for Assessment of Tetracycline Resistance (tet) Genes in Antibiotic-Resistant Soil Bacteria and the Ecological Implications

Antibiotics are becoming increasingly prevalent in bacterial communities due to clinical and agricultural misuse and overuse in their environment. As exposure increases, so does the incidence of microbial resistance. Such is the case with bacterial resistance to tetracyclines, a phenotype often acquired through the horizontal gene transfer of tet genes between bacteria. The objective of this project was to analyze the bacterial diversity of tet resistance genes in soil from Miami-Dade County. Bacterial isolates were Gram-stained and the Kirby-Bauer antibiotic disk diffusion test was performed to determine each bacterium’s degree of resistance. The 16S rRNA gene from antibiotic-resistant isolates was amplified by PCR and sequenced to identify the isolates. All isolates’ tet genes were amplified by multiplex PCR, sequenced, and compared. Among eight isolates, three distinct species were positively identified based on their 16S rRNA sequences and four distinct tet genes were identified, though all tested susceptible to tetracycline via the Kirby-Bauer test. This project clarifies some aspects of the ecology of antibiotic resistance genes, their natural ecological function and the potential for the expansion of intrinsic multi-antibiotic resistance into new ecosystems and/or hosts.

Enhanced Growth of Tetracycline-susceptible Soil Bacteria Treated with Iron and Oxytetracycline

Antibiotic resistance has become an important area of research because of the excessive use of antibiotics in clinical and agricultural settings that are driving the evolution of antibiotic resistant bacteria. However, drug tolerance is a naturally occurring phenomenon in soil communities, and is often linked to those soils that are exposed to heavy metals as well as antibiotics. Resistance to antibiotics maybe coupled with resistance to heavy metals in soil bacteria through efflux pumps that can be regulated by iron. Although considered s a heavy metal, iron is an essential component of life that regulates gene expression through the Ferric Uptake Regulator (Fur) protein. This master regulator protein is known to control siderophore production, and other biological pathways. As a suspected controller of biofilm formation, the role of Fur in environmental antibiotic resistance may be greater than is currently realized. In this study, we sought to explore a potential Fur-regulated drug tolerance pathway by understanding the response of soil bacteria when stressed with oxytetracycline and iron. Bacteria were collected from two locations in Miami Dade County. Isolates were first tested using Kirby-Bauer Disk Diffusion tests for antibiotic resistance/susceptibility and identified by 16S rDNA sequencing. A 96-well growth assay was developed to measure planktonic cell growth with 3 mM FeCl3, Oxytetracycline HCl, and the combination treatments. A Microtiter Dish Biofilm Formation Assay was employed and Fur diversity was evaluated. Tetracycline-susceptible bacterial isolates developed drug resistance with iron supplementation, but iron did not enhance biofilm formation. Development of a Fur-dependent drug resistance may be selected for, but further study is required to evaluate Fur evolution in the studied isolates. Gene expression analysis is also needed to further understand the ecological role of Fur and antibiotic resistance.

Biogeochemical Effects of Simulated Sea Level Rise on Carbon Loss in an Everglades Mangrove Peat Soil

Saltwater intrusion and inundation can affect soil microbial activity, which regulates the carbon (C) balance in mangroves and helps to determine if these coastal forests can keep pace with sea level rise (SLR). This study evaluated the effects of increased salinity (+15 ppt), increased inundation (−8 cm), and their combination, on soil organic C loss from a mangrove peat soil (Everglades, Florida, USA) under simulated tides. Soil respiration (CO2 flux), methane (CH4) flux, dissolved organic carbon (DOC) production, and porewater nutrient concentrations were quantified. Soil respiration was the major pathway of soil organic C loss (94–98%) and was approximately 90% higher in the control water level than the inundated treatment under elevated salinity. Respiration rate increased with water temperature, but depended upon salinity and tidal range. CH4 flux was minimal, while porewater DOC increased with a concomitant, significant decline in soil bulk density under increased inundation. Porewater ammonium increased (73%) with inundation and soluble reactive phosphorus increased (32%) with salinity. Overall, the decline in soil organic C mineralization from combined saltwater intrusion and prolonged inundation was not significant, but results suggest SLR could increase this soil’s susceptibility to peat collapse and accelerate nutrient and DOC export to adjacent Florida Bay.

Effect of Water Management on Interannual Variation in Bulk Soil Properties from the Eastern Coastal Everglades

We examined interannual variation in soil properties from wetlands occurring in adjacent drainage basins from the southeastern Everglades. Triplicate 10-cm soil cores were collected, homogenized, and analyzed during the wet season 2006–2010 from five freshwater sawgrass wetland marshes and three estuarine mangrove forests. Soil bulk density from the Taylor Slough basin ranged from 0.15 gm-cm−3 to 0.5 gm-cm−3, was higher than from the Panhandle basin every year, and generally increased throughout the study period. Organic matter as a percent loss on ignition ranged from 7 % to 12 % from freshwater marshes and from 13 % to 56 % from estuarine mangroves. Extractable iron in soils was similar among drainage basins and wetland types, typically ranging from 0.6 to 2.0 g Fe kg−1. In contrast, inorganic sulfur was on average over four times higher from estuarine soils relative to freshwater, and was positively correlated with soil organic matter. Finally total soil phosphorus (P) was lower in freshwater soils relative to estuarine soils (84 ± 5 versus 326 ± 32 mg P kg−1). Total P from the freshwater marshes in the Panhandle basin rose throughout the study period from 54.7 ± 8.4 to 107 ± 17 mg P kg−1, a possible outcome of differences in water management between drainage basins.

Changes of Soil Biogeochemistry under Native and Exotic Plants Species

Invasive plant species are major threats to the biodiversity and ecosystem stability. The purpose of this study is to understand the impacts of invasive plants on soil nutrient cycling and ecological functions. Soil samples were collected from rhizosphere and non-rhizosphere of both native and exotic plants from three genera, Lantana, Ficus and Schinus, at Tree Tops Park in South Florida, USA. Experimental results showed that the cultivable bacterial population in the soil under Brazilian pepper (invasive Schinus) was approximately ten times greater than all other plants. Also, Brazilian pepper lived under conditions of significantly lower available phosphorus but higher phosphatase activities than other sampled sites. Moreover, the respiration rates and soil macronutrients in rhizosphere soils of exotic plants were significantly higher than those of the natives (Phosphorus, p=0.034; Total Nitrogen, p=0.0067; Total Carbon, p=0.0243). Overall, the soil biogeochemical status under invasive plants was different from those of the natives.

Buckwheat as a Cover Crop in Florida: Mycorrhizal Status, Soil Analysis, and Economic Assessment

This thesis analyses buckwheat as a cover crop in Florida. The study was designed to demonstrate: soil enrichment with nutrients, mycorrhizal arbuscular fungi interactions, growth in different soil types, temperature limitations in Florida, and economic benefits for farmers. Buckwheat was planted at the FIU organic garden (Miami, FL) in early November and harvested in middle December. After incorporation of buckwheat residues, soil analyses indicated the ability of buckwheat to enrich soil with major nutrients, in particular, phosphorus. Symbiosis with arbuscular mycorrhizal fungi increased inorganic phosphorus uptake and plant growth. Regression analysis on aboveground buckwheat biomass weight and soil characteristics showed that high soil pH was the major limiting factor that affected buckwheat growth. Spatial analysis illustrated that buckwheat could be planted in South Florida throughout the year but might not be planted in North and Central Florida in winter. An economic assessment proved buckwheat to be a profitable cover crop.

Influence of Soil Biogeochemical Properties on the Invasiveness of Old World Climbing Fern (Lygodium microphyllum)

The state of Florida has one of the most severe exotic species invasion problems in the United States, but little is known about their influence on soil biogeochemistry. My dissertation research includes a cross-continental field study in Australia, Florida, and greenhouse and growth chamber experiments, focused on the soil-plant interactions of one of the most problematic weeds introduced in south Florida, Lygodium microphyllum (Old World climbing fern). Analysis of field samples from the ferns introduced and their native range indicate that L microphyllum is highly dependent on arbuscular mycorrhizal fungi (AMF) for phosphorus uptake and biomass accumulation. Relationship with AMF is stronger in relatively dry conditions, which are commonly found in some Florida sites, compared to more common wet sites where the fern is found in its native Australia. In the field, L. microphyllum is found to thrive in a wide range of soil pH, texture, and nutrient conditions, with strongly acidic soils in Australia and slightly acidic soils in Florida. Soils with pH 5.5 - 6.5 provide the most optimal growth conditions for L. microphyllum, and the growth declines significantly at soil pH 8.0, indicating that further reduction could happen in more alkaline soils. Comparison of invaded and uninvaded soil characteristics demonstrates that L. microphyllum can change the belowground soil environment, with more conspicuous impact on nutrient-poor sandy soils, to its own benefit by enhancing the soil nutrient status. Additionally, the nitrogen concentration in the leaves, which has a significant influence in the relative growth rate and photosynthesis, was significantly higher in Florida plants compared to Australian plants. Given that L. microphyllum allocates up to 40% of the total biomass to rhizomes, which aid in rapid regeneration after burning, cutting or chemical spray, hence management techniques targeting the rhizomes look promising. Over all, my results reveal for the first time that soil pH, texture, and AMF are major factors facilitating the invasive success of L. mcirophyllum. Finally, herbicide treatments targeting rhizomes will most likely become the widely used technique to control invasiveness of L. microphyllum in the future. However, a complete understanding of the soil ecosystem is necessary before adding any chemicals to the soil to achieve a successful long-term invasive species management strategy.