Influence of graphene oxide additives on the NF separation of triazine-based H2S scavenging compounds using advanced membrane technology.

This work proposes an innovative approach for the membrane separation of spent and unspent H2S scavengers (SUS) derived from the application of MEA-triazine in offshore oil and gas production. Modified nanofiltration membranes were fabricated by incorporating graphene oxide (GO) and polyvinyl alcohol (PVA) into a thin film composite (TFC) to obtain a thin film nanocomposite (TFN) with enhanced permeability. In addition, various immobilization strategies for GO were investigated. The performance of the membranes and the effect of the GO loading were evaluated in terms of permeability, fouling propensity, and rejection of key components of the SUS, i.e., MEA-triazine (unspent scavenger), dithiazine (spent scavenger), and monoethanolamine, operating on a sample of SUS wastewater obtained from an offshore oil and gas platform. Various characterization techniques, such as contact angle, FTIR, XRD, SEM, TGA, and AFM, were employed to evaluate the structure, composition, and hydrophilicity of the membrane. The results show a remarkable increase in permeability (from 0.22 Lm-2 h-1 bar-1 for the TFC to 5.8 Lm-2 h-1 bar-1 for the TFN membranes), due to the enhanced hydrophilicity from GO incorporation. The strong interfacial interaction between GO and PVA within the TFN membrane results in negligible nanofiller leaching. The incorporation of GO moderately increases the rejection of the unspent scavenger (63%-73%, 62%-79%, 62%-80%, and 68%-76%), while drastically increasing the rejection of the spent scavenger, which is approximately null for the TFC membrane without GO and increases up to 58% in the TFN membrane with GO. Therefore, while the proposed membranes cannot be used for the selective separation of the unspent form the spent scavenger, they can achieve substantial recovery of all the key components contained in the SUS to avoid their discharge into the sea.

Reducing the environmental impact of offshore H2S scavenging wastewater via hydrothermal oxidation.

The discharge of H2S scavenging wastewaters, containing spent and unspent scavengers (SUS), into the marine environment is a large contributor to the environmental impact of offshore oil and gas production. Hydrothermal oxidation (HTO) can be a viable method for on-site treatment of the SUS before discharge, but the effect of the process on the ecotoxicity of the effluent has not been investigated so far. The aim of this study was to investigate the potential of the HTO technology in reducing the environmental impact by linking the chemical process design with ecotoxicity reduction. For this, we combined HTO experiments on a SUS sample from an oil and gas platform in the North Sea with whole effluent ecotoxicity evaluation before and after the treatment. The HTO process was carried out under excess of oxygen, for temperatures and pressures in the range 199 to 350°C and 83 to 228 bar, respectively, and for reaction times of 5 to 360 min. Initially, the SUS sample exhibited very high ecotoxicity, which was drastically reduced by the HTO process. More specifically, the ecotoxicity towards bacteria was reduced more than 90% for all HTO conditions, while the reduction in algal toxicity was in the range 48% to 66%, 59% to 86% and 60% to 82% at reaction temperatures of 199°C, 279°C, and 350°C, respectively. Furthermore, this work shows how typical wastewater chemical analyses, such as COD and TOC, and ecotoxicity tests towards different organisms provide complementary information, which should be used in combination to optimize operating conditions of the HTO process.

Combining reverse osmosis and microbial degradation for remediation of drinking water contaminated with recalcitrant pesticide residue.

Groundwater contamination by recalcitrant organic micropollutants such as pesticide residues poses a great threat to the quality of drinking water. One way to remediate drinking water containing micropollutants is to bioaugment with specific pollutant degrading bacteria. Previous attempts to augment sand filters with the 2,6-dichlorobenzamide (BAM) degrading bacterium Aminobacter niigataensis MSH1 to remediate BAM-polluted drinking water initially worked well, but the efficiency rapidly decreased due to loss of degrader bacteria. Here, we use pilot-scale augmented sand filters to treat retentate of reverse osmosis treatment, thus increasing residence time in the biofilters and potentially nutrient availability. In a first pilot-scale experiment, BAM and most of the measured nutrients were concentrated 5-10 times in the retentate. This did not adversely affect the abundances of inoculated bacteria and the general prokaryotic community of the sand filter presented only minor differences. On the other hand, the high degradation activity was not prolonged compared to the filter receiving non-concentrated water at the same residence time. Using laboratory columns, it was shown that efficient BAM degradation could be achieved for >100 days by increasing the residence time in the sand filter. A slower flow may have practical implications for the treatment of large volumes of water, however this can be circumvented when treating only the retentate water equalling 10-15% of the volume of inlet water. We therefore conducted a second pilot-scale experiment with two inoculated sand filters receiving membrane retentate operated with different residence times (22 versus 133 min) for 65 days. While the number of MSH1 in the biofilters was not affected, the effect on degradation was significant. In the filter with short residence time, BAM degradation decreased from 86% to a stable level of 10-30% degradation within the first two weeks. The filter with the long residence time initially showed >97% BAM degradation, which only slightly decreased with time (88% at day 65). Our study demonstrates the advantage of combining membrane filtration with bioaugmented filters in cases where flow rate is of high importance.

Speed dating for enzymes! Finding the perfect phosphopantetheinyl transferase partner for your polyketide synthase.

The biosynthetic pathways for the fungal polyketides bikaverin and bostrycoidin, from Fusarium verticillioides and Fusarium solani respectively, were reconstructed and heterologously expressed in S. cerevisiae alongside seven different phosphopantetheinyl transferases (PPTases) from a variety of origins spanning bacterial, yeast and fungal origins. In order to gauge the efficiency of the interaction between the ACP-domains of the polyketide synthases (PKS) and PPTases, each were co-expressed individually and the resulting production of target polyketides were determined after 48 h of growth. In co-expression with both biosynthetic pathways, the PPTase from Fusarium verticillioides (FvPPT1) proved most efficient at producing both bikaverin and bostrycoidin, at 1.4 mg/L and 5.9 mg/L respectively. Furthermore, the remaining PPTases showed the ability to interact with both PKS's, except for a single PKS-PPTase combination. The results indicate that it is possible to boost the production of a target polyketide, simply by utilizing a more optimal PPTase partner, instead of the commonly used PPTases; NpgA, Gsp and Sfp, from Aspergillus nidulans, Brevibacillus brevis and Bacillus subtilis respectively.

Production and Selectivity of Key Fusarubins from Fusarium solani due to Media Composition.

Natural products display a large structural variation and different uses within a broad spectrum of industries. In this study, we investigate the influence of carbohydrates and nitrogen sources on the production and selectivity of production of four different polyketides produced by Fusarium solani, fusarubin, javanicin, bostrycoidin and anhydrofusarubin. We introduce four different carbohydrates and two types of nitrogen sources. Hereafter, a full factorial design was applied using combinations of three levels of sucrose and three levels of the two types of nitrogen. Each combination displayed different selectivity and production yields for all the compounds of interest. Response surface design was utilized to investigate possible maximum yields for the surrounding combinations of media. It was also shown that the maximum yields were not always the ones illustrating high selectivity, which is an important factor for making purification steps easier. We visualized the production over time for one of the media types, illustrating high yields and selectivity.

Heterologous Expression of the Core Genes in the Complex Fusarubin Gene Cluster of Fusarium Solani.

Through stepwise recreation of the biosynthetic gene cluster containing PKS3 from Fusarium solani, it was possible to produce the core scaffold compound of bostrycoidin, a red aza-anthraquinone pigment in Saccharomyces cerevisiae. This was achieved through sequential transformation associated recombination (TAR) cloning of FvPPT, fsr1, fsr2, and fsr3 into the pESC-vector system, utilizing the inducible bidirectional galactose promoter for heterologous expression in S. cerevisiae. The production of the core metabolite bostrycoidin was investigated through triplicate growth cultures for 1-4 days, where the maximum titer of bostrycoidin was achieved after 2 days of induction, yielding 2.2 mg/L.

Simulation of electrochemical properties of naturally occurring quinones.

Quinones are produced in organisms and are utilized as electron transfer agents, pigments and in defence mechanisms. Furthermore, naturally occurring quinones can also be cytotoxins with antibacterial properties. These properties can be linked to their redox properties. Recent studies have also shown that quinones can be utilized in flow battery technology, though naturally occurring quinones have not yet been investigated. Here, we have analyzed the properties of 990 different quinones of various biological sources through a computation approach to determine their standard reduction potentials and aqueous solubility. The screening was performed using the PBE functional and the 6-31G** basis set, providing a distribution of reduction potentials of the naturally occurring quinones varying from - 1.4 V to 1.5 V vs. the standard hydrogen electrode. The solvation energy for each quinone, which indicates the solubility in aqueous solution, was calculated at the same level. A large distribution of solubilities was obtained, containing both molecules that show tendencies of good solubilities and molecules that do not. The solubilities are dependent on the nature of the side groups and the size of the molecules. Our study shows that the group containing the quinones of fungal origin, which is also the largest of the groups considered, has the largest antimicrobial and electrochemical potential, when considering the distribution of reduction potentials for the compounds.

Synergy optimization for the removal of dye and pesticides from drinking water using granular activated carbon particles in a 3D electrochemical reactor.

The combination of adsorption on particulate materials and electrochemical oxidation in 3D electrochemical systems is potentially a very efficient process for the treatment of micropollutants in water. This paper presents results on the use of granular activated carbon as particulate material in the process and treatment of the dye 4-nitrosodimethylaniline and pesticides MCPA (2-methyl-4-chlorophenoxyacetic acid), MCPP (2-methyl-4-chlorophenoxypropionic acid), and the pesticide transformation product BAM (2,6-dichloro-benzamide) in drinking water. 4-nitrosodimethylaniline was used to investigate influential factors as loading of GAC in a batch electrochemical setup and strength of the electric field in a flow cell recirculation batch setup. Results showed that compared to previous studies in distilled water, only additive effects were found in batch setup, and higher electric field strength was needed in the flow cell setup to achieve slight synergy (~ 5%). Reasons were likely due to the indirect oxidation pathways mediated by the anodic chloride oxidation induced by the content of chloride in the drinking water. On MCPA, MCPP and BAM synergies from 28 to 38% were measured in the batch setup, but in the flow cell, results ranged from additive effects (~ 0%) up to 70%. Considering the low price and widespread availability of granular activated carbon, the gain in process removal rates achieved in the combined 3D electrochemical reactor is of interest compared to the individual processes.

Solubility and reactivity of surfactant-enhanced alkaline hydrolysis of organophosphorus pesticide DNAPL.

The study presented in this paper evaluated the effectiveness of surfactants in enhancing mass removal of organophosphorus pesticides (OPPs) from soil under highly alkaline conditions and potential for enhancing in situ alkaline hydrolysis for treatment of OPPs, particularly parathion (EP3) and methyl parathion (MP3). In control and surfactant experiments, hydrolysis products EP2 acid, MP2 acid, and PNP were formed in non-stoichiometric amounts indicating instability of these compounds. MP3 and malathion were found to have faster hydrolysis rates than EP3 under the conditions studied. All surfactants evaluated increased solubility of OPPs under alkaline conditions with four nonionic alcohol ethoxylate products providing the greater affect over the polyglucosides, sulfonate, and propionate surfactants evaluated. The alcohol ethoxylates were shown to provide substantial mass removal of OPPs from soil. Hydrolysis rates were typically slower in the presence of surfactant, despite the relatively higher aqueous concentrations of OPPs; this was likely due to micellar solubilization of the OPPs which were therefore less accessible for hydrolysis. The results of this study support the use of surfactants for contaminant mass removal from soil, particularly under alkaline conditions, and may have implications for use of some surfactants in combination with other technologies for treatment of OPPs.

A novel hybrid concept for implementation in drinking water treatment targets micropollutant removal by combining membrane filtration with biodegradation.

Groundwater extracted for drinking water production is commonly treated by aeration and sand filtration. However, this simple treatment is typically unable to remove pesticide residues. As a solution, bioaugmentation of sand filter units (i.e., the addition of specific degrader strains) has been proposed as an alternative "green" technology for targeted pesticide removal. However, the introduced degraders are challenged by (i) micropollutant levels of target residue, (ii) the oligotrophic environment and (iii) competition and predation by the native microorganisms, leading to loss of population and degradation potential. To overcome these challenges, we propose the introduction of a novel hybrid treatment step to the overall treatment process in which reverse osmosis filtration and biodegradation are combined to remove a target micropollutant. Here, the reverse osmosis produces a concentrated retentate that will act as a feed to a dedicated biofilter unit, intended to promote biodegradation potential and stability of an introduced degrader. Subsequently, the purified retentate will be re-mixed with the permeate from reverse osmosis, for re-mineralization and downstream consumption. In our study, we investigated the effect of reverse osmosis retentates on the degradation potential of an introduced degrader. This paper provides the first promising results of this hybrid concept using the 2,6-dichlorobenzamide (BAM)-degrading bacteria Aminobacter sp. MSH1 in batch experiments, spiked with radiolabeled BAM. The results showed an increased degradation potential of MSH1 in retentate waters versus untreated water. Colony-forming units and qPCR showed a stable MSH1 population, despite higher concentrations of salts and metals, and increased growth of native bacteria.

PAHs contamination levels in the breast milk of Ghanaian women from an e-waste recycling site and a residential area.

Breast milk samples from 128 primipararae and multiparae Ghanaian women were screened for Polycyclic Aromatic Hydrocarbons (PAHs) from 2014 and 2016. These were breast milk from women residing or working around an electronic waste recycling site and a reference area (a residential area). This research is aimed at assessing PAHs levels in human milk samples from some Ghanaian mothers, prediction of the sources of these PAHs and the probable carcinogenic and mutagenic risks to infants. PAHs in the breast milk were analyzed using a gas chromatography coupled with a mass spectrometer (GC-MS/MS). A total of 18 PAH congeners were identified in the human milk samples with a total range between

Assessment of PCBs and exposure risk to infants in breast milk of primiparae and multiparae mothers in an electronic waste hot spot and non-hot spot areas in Ghana.

The aim of the study was to assess the levels of PCBs in the breast milk of some Ghanaian women at suspected hotspot and relatively non-hotspot areas and to find out if the levels of these PCBs pose any risk to the breastfed infants. A total of 128 individual human breast milk were sampled from both primiparae and multiparae mothers. The levels of PCBs in the milk samples were compared. Some of these mothers (105 individuals) work or reside in and around Agbogbloshie (hot-spot), the largest electric and electronic waste dump and recycling site in Accra, Ghana. Others (23 donor mothers) also reside in and around Kwabenya (non-hotspot) which is a mainly residential area without any industrial activities. Samples were analyzed using GC-MS/MS. The total mean levels and range of Σ7PCBs were 3.64ng/glipidwt and ˂LOD-29.20ng/glipidwt, respectively. Mean concentrations from Agbogbloshie (hot-spot area) and Kwabenya (non-hotspot areas) were 4.43ng/glipidwt and 0.03ng/glipidwt, respectively. PCB-28 contributed the highest of 29.5% of the total PCBs in the milk samples, and PCB-101 contributed the lowest of 1.74%. The estimated daily intake of PCBs and total PCBs concentrations in this work were found to be lower as compared to similar studies across the world. The estimated hazard quotient using Health Canada's guidelines threshold limit of 1µg/kgbw/day showed no potential health risk to babies. However, considering minimum tolerable value of 0.03µg/kgbw/day defined by the Agency for Toxic Substances and Disease Registry (ATSDR), the values of some mothers were found to be at the threshold limit. This may indicate a potential health risk to their babies. Mothers with values at the threshold levels of the minimum tolerable limits are those who work or reside in and around the Agbogbloshie e-waste site.

The influence of cosolvent and heat on the solubility and reactivity of organophosphorous pesticide DNAPL alkaline hydrolysis.

The presented research concerned the compatibility of cosolvents with in situ alkaline hydrolysis (ISAH) for treatment of organophosphorous (OPP) pesticide contaminated sites. In addition, the influence of moderate temperature heat increments was studied as a possible enhancement method. A complex dense non-aqueous phase liquid (DNAPL) of primarily parathion (~50 %) and methyl parathion (~15 %) obtained from the Danish Groyne 42 site was used as a contaminant source, and ethanol and propan-2-ol (0, 25, and 50 v/v%) was used as cosolvents in tap water and 0.34 M NaOH. Both cosolvents showed OPP solubility enhancement at 50 v/v% cosolvent content, with slightly higher OPP concentrations reached with propan-2-ol. Data on hydrolysis products did not show a clear trend with respect to alkaline hydrolysis reactivity in the presence of cosolvents. Results indicated that the hydrolysis rate of methyl-parathion (MP3) decreased with addition of cosolvent, whereas the hydrolysis rate of ethyl-parathion (EP3) remained constant, and overall indications were that the hydrolysis reactions were limited by the rate of hydrolysis rather than NAPL dissolution. In addition to cosolvents, the influence of low-temperature heating on ISAH was studied. Increasing reaction temperature from 10 to 30 °C provided an average rate of hydrolysis enhancement by a factor of 1.4-4.8 dependent on the base of calculation. When combining 50 v/v% cosolvent addition and heating to 30 °C, EP3 solubility was significantly enhanced and results for O,O-diethyl-thiophosphoric acid (EP2 acid) showed a significant enhancement of hydrolysis as well. However, this could not be supported by para-nitrophenol (PNP) data indicating the instability of this product in the presence of cosolvent.

Study of degradation intermediates formed during electrochemical oxidation of pesticide residue 2,6-dichlorobenzamide (BAM) in chloride medium at boron doped diamond (BDD) and platinum anodes.

For electrochemical oxidation to become applicable in water treatment outside of laboratories, a number of challenges must be elucidated. One is the formation and fate of degradation intermediates of targeted organics. In this study the degradation of the pesticide residue 2,6-dichlorobenzamide, an important groundwater pollutant, was investigated in a chloride rich solution with the purpose of studying the effect of active chlorine on the degradation pathway. To study the relative importance of the anodic oxidation and active chlorine oxidation in the bulk solution, a non-active BDD and an active Pt anode were compared. Also, the effect of the active chlorine oxidation on the total amount of degradation intermediates was investigated. We found that for 2,6-dichlorobenzamide, active chlorine oxidation was determining for the initial step of the degradation, and therefore yielded a completely different set of degradation intermediates compared to an inert electrolyte. For the Pt anode, the further degradation of the intermediates was also largely dependent on active chlorine oxidation, while for the BDD anode anodic oxidation was most important. It was also found that the presence of active chlorine led to fewer degradation intermediates compared to treatment in an inert electrolyte.

Development of a spectrophotometric method for on-site analysis of peroxygens during in-situ chemical oxidation applications.

Activated peroxygens are frequently used as active agents in in-situ chemical oxidation (ISCO) contaminated site remediation applications, and fast and simple quantitative analysis of these species on site is necessary. In this work, the use of a spectrophotometric method based on classic iodometric titration is studied for quantitative analysis of S2O8(2-) and H2O2. Instead of a back-titration step, the absorbance of the yellow iodide colour was measured at 352 nm in the presence of a bicarbonate buffer. A linear calibration curve was obtained from 0 to 0.1 mM for both S2O8(2-) and H2O2. By dilution, the method can be used for all concentrations typically applied in the field. Concerning pH dependence, neutral pH levels caused no significant error whereas pH levels above 8 caused a 9% and 6% deviation from the theoretical peroxygen concentrations. Furthermore, the method showed little dependence on other matrix components, and absorbance was stable (<2% change) for more than a week. Overall, the method proved to be fast and simple, which are important features for a field method.

Study of degradation intermediates formed during electrochemical oxidation of pesticide residue 2,6-dichlorobenzamide (BAM) at boron doped diamond (BDD) and platinum-iridium anodes.

Electrochemical oxidation is a promising technique for degradation of otherwise recalcitrant organic micropollutants in waters. In this study, the applicability of electrochemical oxidation was investigated concerning the degradation of the groundwater pollutant 2,6-dichlorobenzamide (BAM) through the electrochemical oxygen transfer process with two anode materials: Ti/Pt90-Ir10 and boron doped diamond (Si/BDD). Besides the efficiency of the degradation of the main pollutant, it is also of outmost importance to control the formation and fate of stable degradation intermediates. These were investigated quantitatively with HPLC-MS and TOC measurements and qualitatively with a combined HPLC-UV and HPLC-MS protocol. 2,6-Dichlorobenzamide was found to be degraded most efficiently by the BDD cell, which also resulted in significantly lower amounts of intermediates formed during the process. The anodic degradation pathway was found to occur via substitution of hydroxyl groups until ring cleavage leading to carboxylic acids. For the BDD cell, there was a parallel cathodic degradation pathway that occurred via dechlorination. The combination of TOC with the combined HPLC-UV/MS was found to be a powerful method for determining the amount and nature of degradation intermediates.

Influence of chloride and carbonates on the reactivity of activated persulfate.

Chloride and carbonates have the potential to impact pathway, kinetics, and efficiency of oxidation reactions, both as radical scavengers and as metal complexing agents. Traditionally, it is assumed that they have an overall negative impact on the activated persulfate performance. This study investigated the influence of carbonates and chloride on the reactivity of persulfate for three different activation techniques to produce reactive free sulfate radicals; heat, alkaline and iron activation. By using p-nitrosodimethylaniline as model target compound, it was demonstrated that iron activation at neutral pH was not affected by Cl(-) or HCO(3)(-), alkaline activation was enhanced by Cl(-) and even more by CO(3)(2-), and heat activation was enhanced by Cl(-), and no effect from HCO(3)(-) was observed. At pH 2 destruction of perchloroethylene by iron activated persulfate was significantly affected by chloride. Reaction rates decreased, but the overall oxidation efficiency was unaffected up to 28 mM Cl(-). The effect of chloride and carbonates is caused by direct attack of produced reactive chlorine, or carbonate species or by catalysis of the propagation reactions resulting in more sulfate radicals. These results show that carbonate and chloride might play an important role in activated persulfate applications and should not strictly be considered as scavengers.

Identification and fate of halogenated PAHs formed during electrochemical treatment of saline aqueous solutions.

Halogenations of polycyclic aromatic hydrocarbons (PAHs) comprise a serious problem, when electrochemical oxidation (EO) is applied for treatment of chloride and bromide containing polluted sea water. In this study, the possible non-polar halogenated byproducts formed were identified in a series of chemical hypochlorination experiments using GC-MS, and the analytical information from these experiments was used in the primary EO treatment tests. An electrochemical cell equipped with a Ti/Pt(90)-Ir(10) anode was used in a batch recirculation setup with naphthalene, pyrene, and fluoranthene as the parent PAHs. Contrary to the chemical hypochlorination experiments, naphthalene as the most soluble compound was the only one to be halogenated in detectable amounts during EO. In a single sodium chloride electrolyte, up to 13% of the initial naphthalene was chlorinated at the peak concentration during treatment before it was subsequently removed. Even small concentrations of added bromide in a mixed electrolyte completely dominated the byproduct pattern with formation of primarily mono brominated naphthalene in peak concentrations up to 30-39% of the initial naphthalene. All of the considered byproducts were despite a more recalcitrant behavior degraded at prolonged treatment times, which need to be applied to ensure a safe discharge of the treated water.