Seasonal differences in trace metal concentrations in the major rivers of the hyper-arid southwestern Andes basins of Peru.

The southern rivers of Peru originate in the Andes Mountains and flow in a southwestern direction to the Pacific Ocean through one of the most hyper-arid regions of the world. During each sub-equatorial summer from December to February, rains and snow melt in the Andes increase the streamflow in these rivers, even as they pass through the 100 km arid zone to the ocean. This study quantified seasonal dynamics of 34 trace metal elements (TM) and other constituent concentrations in four southern river basins of Peru (Chili-Quilca, Tambo, Camana-Majes-Colca, and Ocoña) during 2019-2020. Consistent with previous studies, we observed that: (1) the river water in the southern basins had relatively high concentrations of B, As, Fe, Al, Mn, P, Pb and Ni, with As the most ubiquitous toxic TM in all the basins, often detected at concentrations surpassing Peruvian and USEPA regulated concentrations; and (2) basins with the most to least toxic TM contamination were the Tambo > Chili-Quilca > Camana-Majes-Colca > Ocoña. Seasonal streamflow strongly influenced the concentrations of twenty TM, with 15 TM (Al, Au, Ba, Cd, Co, Cu, Fe, Gd, Mn, Ni, P, Pb, Ti, Yb and Zr) consistently higher in the wet season, and with As, B, Ge, Li, and Pd higher in the dry season. Our results improve the understanding of seasonal variability and vulnerability in western Andes superficial water sources, which are highly influenced by both local geogenic and anthropogenic conditions. A Spanish translation of this paper is available in the online Supplementary Material.

Anion Exchange on Cationic Surfactant Micelles, and a Speciation Model for Estimating Anion Removal on Micelles during Ultrafiltration of Water.

Surfactant micelles combined with ultrafiltration can partially, or sometimes nearly completely, separate various ionic and nonionic pollutants from water. To this end, the selectivity of aqueous micelles composed of either cetyltrimethylammonium (CTA+) bromide or cetylpyridinium (CP+) chloride toward many environmentally relevant anions (IO3-, F-, Cl-, HCO3-, NO2-, Br-, NO3-, H2PO4-, HPO42-, SO42-, and CrO42-) was investigated. Selectivity coefficients of CTA+ micelles (with respect to Br-) and CP+ micelle (with respect to Cl-) for these anions were evaluated using a simple thermodynamic ion exchange model. The sequence of anion affinity for the CTA+ micelles and for the CP+ micelles were the same, with decreasing affinity occurring in the order of: CrO42- > SO42- > HPO42- > NO3- > Br- > NO2- > Cl- > HCO3- > H2PO4- ≈ F-. From the associated component mass balance and ion exchange (i.e., mass action) equations, an overall speciation model was developed to predict the distribution of all anions between the aqueous and micellar pseudophase for complex ionic mixtures. Experimental results of both artificial and real surface waters were in good agreement to model predictions. Further, the results indicated that micelles combined with ultrafiltration may be a potential technology for nutrient and other pollutant removal from natural or effluent waters.

Calibration and application of an automated seepage meter for monitoring water flow across the sediment-water interface.

The advective flow of sediment pore water is an important parameter for understanding natural geochemical processes within lake, river, wetland, and marine sediments and also for properly designing permeable remedial sediment caps placed over contaminated sediments. Automated heat pulse seepage meters can be used to measure the vertical component of sediment pore water flow (i.e., vertical Darcy velocity); however, little information on meter calibration as a function of ambient water temperature exists in the literature. As a result, a method with associated equations for calibrating a heat pulse seepage meter as a function of ambient water temperature is fully described in this paper. Results of meter calibration over the temperature range 7.5 to 21.2 °C indicate that errors in accuracy are significant if proper temperature-dependence calibration is not performed. The proposed calibration method allows for temperature corrections to be made automatically in the field at any ambient water temperature. The significance of these corrections is discussed.

Light-independent reactive oxygen species (ROS) formation through electron transfer from carboxylated single-walled carbon nanotubes in water.

Promising developments in application of carbon nanotubes (CNTs) have raised concern regarding potential biological and environmental effects upon their inevitable release to the environment. Although some CNTs have been reported to generate reactive oxygen species (ROS) under light, limited information exists on ROS generation by these materials in the dark. In this study, generation of ROS was examined, initiated by electron transfer from biological electron donors through carboxylated single-walled carbon nanotubes (C-SWCNT) to molecular oxygen in water in the dark. In the presence of C-SWCNT, the oxidation of NADH (ß-nicotinamide adenine dinucleotide, reduced form) and DTTre (DL-dithiothreitol, reduced form) was confirmed by light absorbance shifts (340 nm to 260 nm during oxidation of NADH to NAD(+), and increased light absorbance at 280 nm during oxidation of DTTre). Production of superoxide anion (O2(•-)) was detected by its selective reaction with a tetrazolium salt (NBT(2+)), forming a formazan product that is visible at 530 nm. A modified acid-quenched N,N-diethyl-p-phenylenediamine (DPD) assay was used to measure the accumulation of H2O2 in C-SWCNT suspensions containing O2 and NADH. In the same suspensions (i.e., containing C-SWCNT, NADH, and O2), pBR322 DNA plasmid was cleaved, although •OH was not detected when using •OH scavenging molecular probes. These results indicate that the oxidation of electron donors by C-SWCNT can be a light-independent source of ROS in water, and that electron shuttling through CNTs to molecular oxygen may be a potential mechanism for DNA damage by this specific CNT and potentially other carbon-based nanomaterials.

Photoreactivity of unfunctionalized single-wall carbon nanotubes involving hydroxyl radical: chiral dependency and surface coating effect.

Single-wall carbon nanotubes (SWCNTs) have a variety of potential and demonstrated applications, and their production rates are increasing rapidly. This increase in production has motivated research on their transport and potential transformation and their toxicity in the environment. In this work, we examined the direct and indirect photoreactivity of SWCNTs under sunlight conditions. We found that the direct photoreactivity of pristine SWCNTs is generally low; however, indirect photoreaction involving ·OH may be significant in natural aquatic environments. Environmental photochemical reactions generating ·OH lead to distinct changes in SWCNT fluorescence efficiency in the near-infrared (NIR) region, Raman spectra, and light attenuation spectra in the UV, visible, and NIR regions, indicating that covalent functionalization of SWCNTs occurs. The reactivity of SWCNTs to ·OH is dependent on the specific chiral structure of the SWCNTs and the surfactant associated with it. An operationally defined second-order rate constant (based on the decrease in NIR fluorescence signals) for all SWCNT chiral species reacting with ·OH was estimated to be (2.91 ± 1.30) × 10(10) M(-1 )s(-1). Our work suggests that photochemical reactions may be a significant transformation pathway of SWCNTs in aquatic systems.

Integrating molecular descriptors for enhanced prediction: Shedding light on the potential of pH to model hydrated electron reaction rates for organic compounds.

Hydrated electron reaction rate constant (ke-aq) is an important parameter to determine reductive degradation efficiency and to mitigate the ecological risk of organic compounds (OCs). However, OC species morphology and the concentration of hydrated electrons (e-aq) in water vary with pH, complicating OC fate assessment. This study introduced the environmental variable of pH, to develop models for ke-aq for 701 data points using 3 descriptor types: (i) molecular descriptors (MD), (ii) quantum chemical descriptors (QCD), and (iii) the combination of both (MD + QCD). Models were screened using 2 descriptor screening methods (MLR and RF) and 14 machine learning (ML) algorithms. The introduction of QCDs that characterized the electronic structure of OCs greatly improved the performance of models while ensuring the need for fewer descriptors. The optimal model MLR-XGBoost(MD + QCD), which included pH, achieved the most satisfactory prediction: R2tra = 0.988, Q2boot = 0.861, R2test = 0.875 and Q2test = 0.873. The mechanistic interpretation using the SHAP method further revealed that QCDs, polarizability, volume, and pH had a great influence on the reductive degradation of OCs by e-aq. Overall, the electrochemical parameters (QCDs, pH) related to the solvent and solute are of significance and should be considered in any future ML modeling that assesses the fate of OCs in aquatic environment.

Slow Sand Filters for the 21st Century: A Review.

Safe drinking water remains a major global challenge, especially in rural areas where, according to UNICEF, 80% of those without access to improved water systems reside. While water, sanitation, and hygiene (WASH)-related diseases and deaths are common outcomes of unsafe water, there is also an economic burden associated with unsafe water. These burdens are most prominent in rural areas in less-developed nations. Slow sand filters (SSFs), or biological sand filters (BSFs), are ideal water treatment solutions for these low-resource regions. SSFs are the oldest municipal drinking water treatment systems and improve water quality by removing suspended particles, dissolved organic chemicals, and other contaminants, effectively reducing turbidity and associated taste and odor problems. The removal of turbidity and dissolved organic compounds from the water enables the use of low-cost disinfection methods, such as chlorination. While the working principles of slow sand filtration have remained the same for over two centuries, the design, sizes, and application of slow sand filters have been customized over the years. This paper reviews these adaptations and recent reports on performance regarding contaminant removal. We specifically address the removal of turbidity and microbial contaminants, which are of great concern to rural populations in developing countries.

Assessing impacts of land-applied manure from concentrated animal feeding operations on fish populations and communities.

Concentrated animal feeding operation (CAFO) manure is a cost-effective fertilizer. In the Midwest, networks of subsurface tile-drains expedite transport of animal hormones and nutrients from land-applied CAFO manure to adjacent waterways. The objective of this study was to evaluate impacts of land-applied CAFO manure on fish populations and communities. Water chemistry including hormone, pesticide, and nutrient concentrations was characterized from study sites along with fish assemblage structure, growth, and endocrine disruption assessed in selected fish species. Although most CAFO water samples had hormone concentrations <1 ng/L, equivalent concentrations for 17ß-E2 and 17α-TB peaked at >30 ng/L each during the period of spawning, hatching, and development for resident fishes. CAFO sites had lower fish species richness, and fishes exhibited faster somatic growth and lower reproductive condition compared to individuals from the reference site. Fathead minnows (Pimephales promelas) exposed to CAFO ditchwater during early developmental stages exhibited significantly skewed sex ratios toward males. Maximum observed hormone concentrations were well above the lowest observable effect concentrations for these hormones; however, complexities at the field scale make it difficult to directly relate hormone concentration and impacts on fish. Complicating factors include the consistent presence of pesticides and nutrients, and the difference in temperature and stream architecture of the CAFO-impacted ditches compared to the reference site (e.g., channelization, bottom substrate, shallow pools, and riparian cover).

Chemical-free pressure washing system as pretreatment to harvest cathode materials.

Recycling cathode materials from spent lithium-ion batteries has the potential to reduce damages to the environment and human health due to hazardous waste treatment, and mitigate supply risks of raw materials. Related political incentives or regulations have led to increased research and development efforts on cathode recycling. Promising approaches include direct recycling and hydrometallurgical processes, where delamination is the first step after collection of cathodes. In this study, we examined a pressure washing system's ability to harvest cathode materials. A high-pressure water jet provides strong forces to overcome the adhesion provided by organic binders. Four factors (water pressure, distance between nozzle and cathode, incident angle of water jet, and nozzle type) were investigated using a 34-1 fractional factorial design to screen important parameters and find the optimal conditions. Compared with other delamination processes where chemical reagents and heating are involved, the chemical-free pressure washing system can achieve separation in a few seconds (∼74 min/m2) at room temperature, which remarkably improves the efficiency of delamination. The particle size of recycled products (D50 of 31.87 µm) is significantly reduced without Al contamination from current collectors or morphological damages. In addition, three types of recycled cathode materials were used as inputs for the acid leaching process. High leaching efficiencies of lithium (>90 %) and cobalt (>85 %) suggest that the pressure washing system could be a practical, economical, and eco-friendly pretreatment process to harvest cathode materials.

Emergency responder and public health considerations for plastic sewer lining chemical waste exposures in indoor environments.

The cured-in-place pipe (CIPP) manufacturing process is used to repair buried pipes, and its waste commonly discharged into the air can enter nearby buildings. Exposure can prompt illness and the need for medical care. A mass balance model was applied to estimate indoor styrene concentrations due to intrusion of CIPP emissions through plumbing under different bathroom ventilation conditions. To better understand building contamination and recommend emergency response actions, calculations to estimate chemical intrusion through plumbing were developed. Field reports and study calculations showed that contractor-applied external pressures during plastic manufacture have and can displace plumbing trap water seals. Modeled styrene vapor concentrations that entered the building (1, 300, 1000 ppm) were similar to those measured at CIPP worksites. Modeling revealed that in some cases, bathroom exhaust fan operation during a CIPP project may increase indoor styrene concentrations due to enhanced entrainment of styrene-laden air from the sink and toilet. However, styrene concentrations decreased with increasing air leakage across the bathroom door due to reduced suction from the plumbing system. CIPP waste discharge should be treated as a hazardous material release and can pose a threat to human health. Immediate building evacuation, respiratory protection, provision of medical assistance, source elimination, and building decontamination are recommended.

Hormone discharges from a midwest tile-drained agroecosystem receiving animal wastes.

Manure is increasingly being viewed as a threat to aquatic ecosystems due to the introduction of natural and synthetic hormones from land application to agricultural fields. In the Midwestern United States, where most agricultural fields are tile-drained, there is little known about hormone release from fields receiving animal wastes. To this end, seven sampling stations (four in subsurface tile drains and three in the receiving ditch network) were installed at a Midwest farm where various types of animal wastes (beef, dairy, and poultry lagoon effluent, dairy solids, and subsurface injection of swine manure) are applied to agricultural fields. Water flow was continuously monitored and samples were collected for hormone analysis during storm events and baseline flow for a 15 month study period. The compounds analyzed included the natural hormones 17α- and 17ß-estradiol, estrone, estriol, testosterone, and androstenedione and the synthetic androgens 17α- and 17ß-trenbolone and trendione. Hormones were detected in at least 64% of the samples collected at each station, with estrone being detected the most frequently and estriol the least. Testosterone and androstendione were detected more frequently than synthetic androgens, which were detected in fewer than 15% of samples. Hormone concentrations in subsurface tile drains increased during effluent irrigation and storm events. Hormones also appeared to persist over the winter, with increased concentrations coinciding with early thaws and snowmelt from fields amended with manure solids. The highest concentration of synthetic androgens (168 ng/L) observed coincided with a snowmelt. The highest concentrations of hormones in the ditch waters (87 ng/L for total estrogens and 52 ng/L for natural androgens) were observed in June, which coincides with the early life stage development period of many aquatic species in the Midwest.

Polyethylene-water partition coefficients for polychlorinated biphenyls: Application of QSPR predictions models with experimental validation.

The water environmental recalcitrance and ecotoxicity caused by polychlorinated biphenyls (PCBs) are international issues of common concern. The partition coefficients with PCBs between low-density polyethylene (LDPE) and water (KPE-w) are significant to assess their environmental transport and/or fate in aquatic environment. Even moderately hydrophobic PCBs, however, possess large KPE-w values, which makes directly experimental measurement labored. Here, based on the combination of quantitative structure-property relationships (QSPRs) and machine-learning algorithms, 10 in-silico models are developed to provide a quick estimate of KPE-w. These models exhibit good goodness-of-fit (R2adj: 0.919-0.975), robustness (Q2LOO: 0.870-0.954) and external prediction performances (Q2ext: 0.880-0.971), providing a speedy feasibility to close data gaps for limited or absent experimental information, especially the RF-2 model. Particularly, an additional experimental verification is performed for models by a rapid and accurate three-phase system (aqueous phase, surfactant micelles and LDPE). The results of the experiments for 16 PCBs show the modeling results agree well with experimental values, within or approaching the residuals of ± 0.3 log unit. Mechanism interpretations imply that the number of chlorine atoms and ortho-substituted chlorines are the great effect parameters for KPE-w. This result also heightens interest in measuring and predicting the KPE-w values of chemicals containing halogen atoms in water.

Development of novel experimental and modelled low density polyethylene (LDPE)-water partition coefficients for a range of hydrophobic organic compounds.

Knowledge about partitioning constants of hydrophobic organic compounds (HOCs) between the polymer and aqueous phases is critical for assessing chemical environmental fate and transport. The conventional experimental method is characterized by large discrepancies in the measured values due to the limited water solubility of HOCs and other associated issues. In the current work, a novel three-phase partitioning system was evaluated to determine accurate low-density polyethylene (LDPE)-water partition coefficients (KPE-w). By adding sufficient surfactant (Brij 30) to form the micellar pseudo-phase within the polymer/water system, the KPE-w values were obtained from a combination of two experimentally measured values, that is, the micelle-water partition coefficient (Kmic-w) and the LDPE-micelle partition coefficient (KPE-mic). The method presented here is capable of shortening the equilibration time to half a month, and avoiding defects of the traditional method with respect to directly measured aqueous phase concentrations. Herein, the KPE-w values were determined for HOCs with little errors. Meanwhile, based on the 120 experimental KPE-w data, several in silico models were also developed as valid extrapolation tools to estimate missing or uncertain values. Analysis of the underlying solubility interactions in the nonionic surfactant micelles were investigated, providing additional support for the reliability of the proposed method.

Effects of ferric ion on the photo-treatment of nonionic surfactant Brij35 washing waste containing 2,2',4,4'-terabromodiphenyl ether.

The effects of ferric iron on the photo-treatment of simulated BDE-47 (2,2',4,4'- terabromodiphenyl ether)-Brij35 (Polyoxyethylene lauryl ether) washing waste were studied to evaluate the influences of ferric iron on BDE-47 removal and Brij35 recovery. The results show that Fe3+ accelerated BDE-47 degradation at lower concentrations (<0.5 mM) but attenuated it at higher concentrations (0.5-5 mM) and that Brij35 loss was increased with increasing Fe3+. These results likely are caused by changes in the rate of •OH production due to the ferric ion, association of Fe3+ and electron transfer from Brij35, and light attenuation at high concentration. The BDE-47 and Brij35 had different degradation rates at different pH values and at different dissolved oxygen concentrations. The BDE-47 products were identified by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The results indicated that BDE-47 transformed into mainly lower-brominated products, a few bromodibenzofurans, some rearrangement products, and some hydroxylated polybrominated diphenyl ethers. A series of Brij35 oxidization products were detected by ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS), including hydroxylation products, carboxylation products, and some hydrophilic chain-breaking products. Brij35 was mainly oxidized by Fe3+ and/or reactive oxygen species (ROS) with the final products of CO2 and H2O. The iron ions apparently cycled from ferric to ferrous ions in the micelles such that the Fe3+-Brij35 complex dominated the main redox reaction, leading to both BDE-47 and Brij35 degradation. It appears that in any applied soil washing system, the ferric ions in the washing waste need to be removed because of the adverse effects on BDE-47 removal and eluate reuse.

Photoreactivity of carboxylated single-walled carbon nanotubes in sunlight: reactive oxygen species production in water.

Very limited information exists on transformation processes of carbon nanotubes in the natural aquatic environment. Because the conjugated pi-bond structure of these materials is efficient in absorbing sunlight, photochemical transformations are a potential fate process with reactivity predicted to vary with their diameter, chirality, number and type of defects, functionalization, residual metal catalyst and amorphous carbon content, and with the composition of the water, including the type and composition of materials that act to disperse them into the aqueous environment. In this study, the photochemical reactions involving colloidal dispersions of carboxylated single-walled carbon nanotubes (SWNT-COOH) in sunlight were examined. Production of reactive oxygen species (ROS) during irradiation occurs and is evidence for potential further phototransformation and may be significant in assessing their overall environmental impacts. In aerated samples exposed to sunlight or to lamps that emit light only within the solar spectrum, the probe compounds, furfuryl alcohol (FFA), tetrazolium salts (NBT2+ and XTT), and p-chlorobenzoic acid (pCBA), were used to indicate production of 1O2, O2.-, and .OH, respectively. All three ROS were produced in the presence of SWNT-COOH and molecular oxygen (3O2). 1O2 production was confirmed by observing enhanced FFA decay in deuterium oxide, attenuated decay of FFA in the presence of azide ion, and the lack of decay of FFA in deoxygenated solutions. Photogeneration of O2.- and .OH was confirmed by applying superoxide dismutase (SOD) and tert-butanol assays, respectively. In air-equilibrated suspensions, the loss of 0.2 mM FFA in 10 mg/L SWNT-COOH was approximately 85% after 74 h. Production of 1O2 was not dependent on pH from 7 to 11; however photoinduced aggregation was observed at pH 3.

Photochemistry of aqueous C60 clusters: wavelength dependency and product characterization.

To construct accurate risk assessment models for engineered nanomaterials, there is urgent need for information on the reactivity (or conversely, persistence) and transformation pathways of these materials in the natural environment. As an important step toward addressing this issue, we have characterized the products formed when aqueous C(60) clusters (nC(60)) are exposed to natural sunlight and also have assessed the wavelengths primarily responsible for phototransformation. Long-wavelength light (λ ≥ 400 nm) isolated from sunlight, was shown to be important in both the phototransformation of nC(60) and in the production of (1)O(2). The significance of visible light in mediating the phototransformation of nC(60) was supported by additional experiments with monochromatic light in which the apparent quantum yield at 436 nm (Φ(436 nm) = (2.08 ± 0.08) × 10(-5)) was comparable to that at 366 nm (Φ(366 nm) = (2.02 ± 0.07) × 10(-5)). LDI-TOF mass spectrometry indicated that most of the photoproducts formed after 947 h of irradiation in natural sunlight retain a 60 atom carbon structure. A combination of (13)C NMR analysis of (13)C-enriched nC(60), X-ray photoelectron spectroscopy and FTIR indicated that photoproducts have olefinic carbon atoms as well as a variety of oxygen-containing functional groups, including vinyl ether and carbonyl or carboxyl groups, whose presence destroys the native π-electron system of C(60). Thus, the photoreactivity of nC(60) in sunlight leads to the formation of water-soluble C(60) derivatives.

Time series analysis of water use and indirect reuse within a HUC-4 basin (Wabash) over a nine year period.

Anthropogenic water use and reuse represent major components of the water cycle. In the context of climate change, water reuse and recycling are considered necessary components for an integrated water management approach. Unplanned, or de facto, indirect water reuse occurs in most of the U.S. river systems, however, there is little real-time documentation of it. Despite the fact that there are national and state agencies that systematically collect data on water withdrawals and wastewater discharges, their databases are organized and managed in a way that makes it challenging to use them for water resource management analysis. The ability to combine reported water data to perform large scale analysis about water use and reuse is severely limited. In this paper, we apply a simple but effective methodology to complete a time series watershed-scale analysis of water use and unplanned indirect reuse for the Wabash River Watershed. Results document the occurrence of indirect water reuse, ranging from 3% to 134%, in a water-rich area of the U.S. The time series analysis shows that reported data effectively describe the water use trends through nine years, from 2009 to 2017, clearly reflecting both anthropogenic and natural events in the watershed, such as the retirement of thermoelectric power plants, and the occurrence of an extreme drought in 2012. We demonstrate the feasibility and significance of using available water datasets to perform large scale water use analysis, describe limitations encountered in the process, and highlight areas for improvement in water data management.

An emerging mobile air pollution source: outdoor plastic liner manufacturing sites discharge VOCs into urban and rural areas.

The in situ manufacture of cured-in-place-pipe (CIPP) plastic liners in damaged sewer pipes is an emerging mobile source of anthropogenic air pollution. Evidence indicates volatile organic compounds (VOCs) can be released before, during, and after manufacture. The chemical composition of a popular uncured styrene-based CIPP resin was examined, along with the VOCs that remained in the new cured composite. The roles of curing temperature and heating time in waste discharged into the air were examined. Uncured resin contained approximately 39 wt% VOCs. Multiple hazardous air pollutants were present, however, 61 wt% of the uncured resin was not chemically identified. A substantial mass of VOCs (8.87 wt%) was emitted into the air during manufacture, and all cured composites contained about 3 wt% VOCs. Some VOCs were created during manufacture. Curing temperature (65.5-93.3 °C) and heating time (25-100 min) did not cause different composite VOC loadings. High styrene air concentrations inhibited the detection of other VOCs in air. It is estimated that tens of tons of VOCs may be emitted at a single CIPP manufacturing site. Regulators should consider monitoring, and potentially regulating, these growing mobile air pollution and volatile chemical product sources as they are operating in urban and rural areas often in close proximity to residential and commercial buildings.

Potential consolidation-induced NAPL migration from coal tar impacted river sediment under a remedial sand cap.

Subaqueous sediment, if capped for remediation purposes, may undergo consolidation due to the increased effective weight of the capping material. The standard Atterberg limits test and a modified drained three-dimensional consolidation test (DTCT) were performed on sediment collected from a river adjacent to a former manufactured gas plant site that contains high concentrations of coal tar. The plastic limit of five sediment samples ranged between 72 and 89%, and the liquid limit ranged between 123 and 194%. The plasticity index ranged from 51 to 122%, with the values among the sediments correlating with the coal tar content (r(2)=0.93). DTCT experiment was performed on 5 cm sediment overlain with 5 cm sand to a maximum applied effective cell pressure of 41.4 kPa. Consolidation increased almost linearly at lower pressures (<13.8 kPa); however, as higher pressures were imposed, the ratio of consolidation per applied pressure decreased. The results of this study suggest that porewater advection, resulting from sediment consolidation, will occur from the sediment to the capping material. Because this water will contain numerous polycyclic aromatic hydrocarbons, measures, such as adding sorptive materials, should be taken to reduce the flux of these compounds.

Decomposition of complexed Pb(II) and subsequent adsorption of Pb(II) with yolk-shell Fe3O4@ hydrous zirconium oxide sphere.

Purification of water containing heavy metals that are complexed by organic chelating agents remains a challenging task. In this study, a yolk-shell Fe3O4@hydrous zirconium oxide (Zr(OH)x) sphere sphere (YHZOs) nanomaterial was evaluated for its ability to remove ethylene diamine tetraacetic acid complexed Pb2+ (Pb-EDTA) from aqueous solution. Specifically, it is hypothesized that upon addition of H2O2, the Fe3O4 core of YHZOs served as a Fenton-type catalyst that results in oxidation of the Pb-complexed EDTA, and the Zr(OH)x shell acted as an adsorbent, removing the released Pb2+ from solution. From an aqueous solution containing 0.1 mM Pb-EDTA at pH 5, 0.5 g/L YHZOs, and 20 mM H2O2, TOC reduction and Pb removal were determined to be 65.3% and 89.8%, respectively. HPLC-MS, IC and continuous flow analyzer results identified major intermediates of EDTA decay to be ethylenediaminetriacetate, (ED3A), ethylenediamine-N,N'-diacetate (ED2A), nitrilotriacetate (NTA), iminodiacetate (IDA), ethylenediamine (EDA), acetic acid, formic acid, oxalic acid, ammonia, and nitrate, with the first 5 species having some affinity to remain complexed to Pb2+. The adsorption of Pb2+ onto the Zr(OH)x shells was confirmed by scanning transmission electron microscopy (STEM) with mapping and X-ray photoelectron spectra (XPS). Moreover, the Pb2+-adsorbed YHZOs could be easily recovered due to their magnetic properties, with the Pb2+ rinsed from them at low pH. Indeed, reused for five cycles showed only minor capacity loss. These findings suggest that the removal of chelated Pb2+ from water, and presumably other heavy metals, by yolk-shell Fe3O4@Zr(OH)x may prove to be a useful technology for some contaminated waters.