Development of a testing protocol for oil solidifier effectiveness evaluation

Chemical countermeasures for oil spill remediation have to be evaluated and approved by the U.S. Environmental Protection Agency before they may be used to remove or control oil discharges. Solidifiers are chemical agents that change oil from a liquid to a solid by immobilizing the oil and bonding the liquid into a solid carpet-like mass with minimal volume increase. Currently, they are listed as Miscellaneous Oil Spill Control Agent in the National Contingency Plan and there is no protocol for evaluating their effectiveness. An investigation was conducted to test the oil removal efficiency of solidifiers using three newly developed testing protocols. The protocols were qualitatively and quantitatively evaluated to determine if they can satisfactorily differentiate effective and mediocre products while still accounting for experimental error. The repeatability of the three protocols was 15.9, 5.1, and 2.7 %. The protocol with the best performance involved measuring the amount of free oil remaining in the water after the solidified product was removed using an ultraviolet–visible spectrophotometer and it was adopted to study the effect of solidifier-to-oil mass ratio, mixing energy, salinity, and beaker size (i.e., area affected by the spill) on solidifier efficiency. Analysis of Variances were performed on the data collected and results indicated that the beaker size increased spreading, which reduced removal efficiency. Mixing speed appears to impart a ceiling effect with no additional benefit provided by the highest level over the middle level. Salinity was found to be mostly an insignificant factor on performance

Distribution of trace metals (Cu, Pb, Ni, Zn) between particulate, colloidal and truly dissolved fractions in wastewater treatment

Issued with Attribution-Non-Commercial-No Derivatives 4.0 (CC BY-NC-ND 4.0)The distribution of Cu, Pb, Ni and Zn between particulate, colloidal and truly dissolved size fractions in wastewater from a trickling filter treatment plant was investigated. Samples of influent, primary effluent, humus effluent, final effluent and sludge holding tank returns were collected and separated into particulate (i.e. > 0.45 μm), colloidal (i.e. 1 kDa to 0.45 μm), and truly dissolved (i.e. < 1 kDa) fractions using membrane filters. In the influent, substantial proportions of Cu (60%), Pb (67%), and Zn (32%) were present in the particulate fraction which was removed in conjunction with suspended particles at the works in subsequent treatment stages. In final effluent, sizeable proportions of Cu (52%), Pb (32%), Ni (44%) and Zn (68%) were found within the colloidal size fraction. Calculated ratios of soluble metal to organic carbon suggest the metal to be adsorbed to or complexed with non-humic macromolecules typically found within the colloidal size range. These findings suggest that technologies capable of removing particles within the colloidal fraction have good potential to enhance metals removal from wastewater

Prediction of bioavailability and toxicity of complex chemical mixtures through machine learning models

Empirical data from a 6-month mesocosms experiment were used to assess the ability and performance of two machine learning (ML) models, including artificial neural network (NN) and random forest (RF), to predict temporal bioavailability changes of complex chemical mixtures in contaminated soils amended with compost or biochar. From the predicted bioavailability data, toxicity response for relevant ecological receptors was then forecasted to establish environmental risk implications and determine acceptable end-point remediation. The dataset corresponds to replicate samples collected over 180 days and analysed for total and bioavailable petroleum hydrocarbons and heavy metals/metalloids content. Further to this, a range of biological indicators including bacteria count, soil respiration, microbial community fingerprint, seeds germination, earthworm's lethality, and bioluminescent bacteria were evaluated to inform the environmental risk assessment. Parameters such as soil type, amendment (biochar and compost), initial concentration of individual compounds, and incubation time were used as inputs of the ML models. The relative importance of the input variables was also analysed to better understand the drivers of temporal changes in bioavailability and toxicity. It showed that toxicity changes can be driven by multiple factors (combined effects), which may not be accounted for in classical linear regression analysis (correlation). The use of ML models could improve our understanding of rate-limiting processes affecting the freely available fraction (bioavailable) of contaminants in soil, therefore contributing to mitigate potential risks and to inform appropriate response and recovery methods

Predicting bioavailability change of complex chemical mixtures in contaminated soils using visible and near-infrared spectroscopy and random forest regression

A number of studies have shown that visible and near infrared spectroscopy (VIS-NIRS) offers a rapid on-site measurement tool for the determination of total contaminant concentration of petroleum hydrocarbons compounds (PHC), heavy metals and metalloids (HM) in soil. However none of them have yet assessed the feasibility of using VIS-NIRS coupled to random forest (RF) regression for determining both the total and bioavailable concentrations of complex chemical mixtures. Results showed that the predictions of the total concentrations of polycyclic aromatic hydrocarbons (PAH), PHC, and alkanes (ALK) were very good, good and fair, and in contrast, the predictions of the bioavailable concentrations of the PAH and PHC were only fair, and poor for ALK. A large number of trace elements, mainly lead (Pb), aluminium (Al), nickel (Ni), chromium (Cr), cadmium (Cd), iron (Fe) and zinc (Zn) were predicted with very good or good accuracy. The prediction results of the total HMs were also better than those of the bioavailable concentrations. Overall, the results demonstrate that VIS-NIR DRS coupled to RF is a promising rapid measurement tool to inform both the distribution and bioavailability of complex chemical mixtures without the need of collecting soil samples and lengthy extraction for further analysis

Hydrodynamics (Reynolds number) determine scaling, nucleation and crystal growth kinetics in membrane distillation crystallisation

Reynolds number (Re) has been previously related to several scaling mitigation and crystallisation strategies that offer distinct hypotheses for how Re may regulate the kinetics of nucleation and crystal growth in membrane crystallisation. Such ambiguity has arisen from the present inability to discretely characterise induction time in membrane systems. This study therefore introduces techniques for the detection of induction time, with measurements used to develop a modified power-law relation between nucleation rate and supersaturation to establish how Re can be used to adjust nucleation kinetics. Increasing Re enhanced mass and heat transfer processes which raised permeate flux. The interfacial supersaturation set by the increase in flux, also modified the supersaturation rate at induction for crystals formed in the bulk solution, providing the first direct evidence that it is the supersaturation level set within the boundary layer which controls primary nucleation in the bulk solution. Bulk nucleation rate can therefore be adjusted in proportion to Re. While the extent of scaling was also determined by the interfacial supersaturation set by Re, its formation was shown to be more dependent on the interfacial diffusion coefficient which regulates solute backtransport and the activation energy for nucleation. Through this work we suggest that the nucleation mechanisms underlying scale formation and bulk crystallisation are distinct. The regulation of nucleation rate in the bulk solution by Re is described analytically through classical nucleation theory, while scaling can be mitigated through operation below a critical threshold supersaturation value that determines the rate and type of scaling that prevails. These seemingly distinct strategies can be combined through modifications to T and dT with Re to suppress scaling and offer refined control over the kinetics of nucleation and crystal growth

Biotransformation and sorption of trace organic compounds in biological nutrient removal treatment systems

This study determined biotransformation rates (kbio) and sorption-distribution coefficients (Kd) for a select group of trace organic compounds (TOrCs) in anaerobic, anoxic, and aerobic activated sludge collected from two different biological nutrient removal (BNR) treatment systems located in Nevada (NV) and Ohio (OH) in the United States (US). The NV and OH facilities operated at solids retention times (SRTs) of 8 and 23 days, respectively. Using microwave-assisted extraction, the biotransformation rates of the chosen TOrCs were measured in the total mixed liquor. Sulfamethoxazole, trimethoprim, and atenolol biotransformed in all three redox regimes irrespective of the activated sludge source. The biotransformation of N, N-diethyl-3-methylbenzamide (DEET), triclosan, and benzotriazole was observed in aerobic activated sludge from both treatment plants; however, anoxic biotransformation of these three compounds was seen only in anoxic activated sludge from NV. Carbamazepine was recalcitrant in all three redox regimes and both sources of activated sludge. Atenolol and DEET had greater biotransformation rates in activated sludge with a higher SRT (23 days), while trimethoprim had a higher biotransformation rate in activated sludge with a lower SRT (8 days). The remaining compounds did not show any dependence on SRT. Lyophilized, heat inactivated sludge solids were used to determine the sorption-distribution coefficients. Triclosan was the most sorptive compound followed by carbamazepine, sulfamethoxazole, DEET, and benzotriazole. The sorption-distribution coefficients were similar across redox conditions and sludge sources. The biotransformation rates and sorption-distribution coefficients determined in this study can be used to improve fate prediction of the target TOrCs in BNR treatment systems

A multi‐component method to determine pesticides in surface water by liquid‐chromatography tandem quadrupole mass spectrometry

Pesticide pollution of surface water is a major concern in many agricultural catchments The development of rapid and accurate methods for determining pesticide concentrations in water samples is, therefore, important. Here we describe a method for the simultaneous analysis of six pesticides (metaldehyde, quinmerac, carbetamide, metazachlor, propyzamide and pendimethalin) in natural waters by direct aqueous injection with liquid chromatography-tandem mass spectrometry. The method validation showed good linearity from 0.2 to 50.0 µg/L with correlation coefficients between 0.995 and 0.999. Method accuracy ranged from 84 to 100% and precision Relative standard deviation (RSD) from 4 to 15%. The limits of detection for the targeted pesticides ranged from 0.03 to 0.36 µg/L. No significant matrix effects on quantification were observed (t-test). The method was tested on water samples from a small arable catchment in eastern England. Peak concentrations for the determinands ranged from 1 to 10 µg/L

Linking bioavailability and toxicity changes of complex chemicals mixture to support decision making for remediation endpoint of contaminated soils

A six-month laboratory scale study was carried out to investigate the effect of biochar and compost amendments on complex chemical mixtures of tar, heavy metals and metalloids in two genuine contaminated soils. An integrated approach, where organic and inorganic contaminants bioavailability and distribution changes, along with a range of microbiological indicators and ecotoxicological bioassays, was used to provide multiple lines of evidence to support the risk characterisation and assess the remediation end-point. Both compost and biochar amendment (p = 0.005) as well as incubation time (p = 0.001) significantly affected the total and bioavailable concentrations of the total petroleum hydrocarbons (TPH) in the two soils. Specifically, TPH concentration decreased by 46% and 30% in Soil 1 and Soil 2 amended with compost. These decreases were accompanied by a reduction of 78% (Soil 1) and 6% (Soil 2) of the bioavailable hydrocarbons and the most significant decrease was observed for the medium to long chain aliphatic compounds (EC16–35) and medium molecular weight aromatic compounds (EC16–21). Compost amendment enhanced the degradation of both the aliphatic and aromatic fractions in the two soils, while biochar contributed to lock the hydrocarbons in the contaminated soils. Neither compost nor biochar affected the distribution and behaviour of the heavy metals (HM) and metalloids in the different soil phases, suggesting that the co-presence of heavy metals and metalloids posed a low risk. Strong negative correlations were observed between the bioavailable hydrocarbon fractions and the ecotoxicological assays suggesting that when bioavailable concentrations decreased, the toxicity also decreased. This study showed that adopting a combined diagnostic approach can significantly help to identify optimal remediation strategies and contribute to change the over-conservative nature of the current risk assessments thus reducing the costs associated with remediation endpoint

Magnetically recoverable TiO2-WO3 photocatalyst to oxidize bisphenol A from model wastewater under simulated solar light

A novel magnetically recoverable, visible light active TiO2-WO3 composite (Fe3O4@SiO2@TiO2-WO3) was prepared to enable the photocatalyst recovery after the degradation of bisphenol A (BPA) under simulated solar light. For comparison, the photocatalytic activity of other materials such as non-magnetic TiO2-WO3, Fe3O4@SiO2@TiO2, TiO2, and the commercial TiO2 P25 was also evaluated under the studied experimental conditions. The structure and morphology of the synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and electron dispersion spectroscopy (EDS). Moreover, Brunauer-Emmett-Teller (BET) surface area and magnetic properties of the samples were determined. The Fe3O4@SiO2@TiO2-WO3 and TiO2-WO3 led to a BPA degradation of 17.50 and 27.92 %, respectively, after 2 h of the simulated solar light irradiation. Even though their activity was lower than that of P25, which degraded completely BPA after 1 h, our catalysts were magnetically separable for their further reuse in the treatment. Furthermore, the influence of the water matrix in the photocatalytic activity of the samples was studied in municipal wastewater. Finally, the identification of reaction intermediates was performed and a possible BPA degradation pathway was proposed to provide a better understanding of the degradation process

Quantification of liquid phase faecal odourants to evaluate membrane technology for wastewater reuse from decentralised sanitation facilities

Public willingness to use decentralised sanitation facilities or arising water products is discouraged due to malodour, preventing improved sanitation practices or water reuse opportunities in low income countries Whilst odour is characterised in the gas phase, it originates in the liquid phase. Consequently, controlling odour at source could prevent gas-phase partitioning and limit produced water contamination. This study therefore developed an analytical method for the quantitation of a range of liquid phase volatile organic compounds (VOCs) classified into eight chemical groups, known to be primary indicators of faecal odour, to provide characterisation of real fluids and to permit evaluation of several potential membrane separation technologies for liquid phase odourant separation. The gas chromatography mass spectrometry method provided quantitation in the range of 0.005 mg L-1 to 100 mg L-1 with instrument detection limits ranging from 0.005 mg L-1 to 0.124 mg L-1. Linear calibration curves were achieved (r2 >0.99) with acceptable accuracy (77-115%) and precision (<15%) for quantitation in the calibration range below 1 mg L 1, and good accuracy (98-104%) and precision (<2%) determined for calibration in the range 1-100 mg L-1. Pre-concentration of real samples was facilitated via solid phase extraction. Subsequent application of the method to the evaluation of two thermally driven membranes based on hydrophilic (polyvinyl alcohol) and hydrophobic (polydimethylsiloxane) polymers evidenced contrasting separation profiles. Importantly, this study demonstrates the methods utility for liquid phase VOC determination which is of use to a range of disciplines, including healthcare professionals, taste and odour specialists and public health engineers