Malcolm Watson

Removal of natural organic matter and arsenic from water by electrocoagulation/flotation continuous flow reactor.

The performance of the laboratory scale electrocoagulation/flotation (ECF) reactor in removing high concentrations of natural organic matter (NOM) and arsenic from groundwater was analyzed in this study. An ECF reactor with bipolar plate aluminum electrodes was operated in the horizontal continuous flow mode. Electrochemical and flow variables were optimized to examine ECF reactor contaminants removal efficiency. The optimum conditions for the process were identified as groundwater initial pH 5, flow rate=4.3 l/h, inter electrode distance=2.8 cm, current density=5.78 mA/cm(2), A/V ratio=0.248 cm(-1). The NOM removal according to UV(254) absorbance and dissolved organic matter (DOC) reached highest values of 77% and 71% respectively, relative to the raw groundwater. Arsenic removal was 85% (6.2 μg As/l) relative to raw groundwater, satisfying the drinking water standards. The specific reactor electrical energy consumption was 17.5 kWh/kg Al. The specific aluminum electrode consumption was 66 g Al/m(3). According to the obtained results, ECF in horizontal continuous flow mode is an energy efficient process to remove NOM and arsenic from groundwater.

Insight into changes during coagulation in NOM reactivity for trihalomethanes and haloacetic acids formation

Natural organic matter (NOM) in raw water can contribute in many ways to the poor quality of drinking water, including the formation of disinfection byproducts such as trihalomethanes (THM) and haloacetic acids (HAA) during disinfection. This paper investigates the role of individual NOM fractions on changes in THM and HAA formation during coagulation with iron chloride (FeCl3) and a combination of polyaluminium chloride and iron chloride (FeCl3/PACl). The dissolved organic carbon (DOC) in the raw water and after coagulation was fractionated into four fractions, based on their hydrophobicity. Fractionation showed that most of the DOC (68%) in the raw water comes from the fulvic acid fraction, yielding 41% of the total THM precursors and 21% of the total HAA precursors. Both coagulants remove the humic acid fraction, but result in different changes to the reactivity of the remaining NOM fractions towards THM and HAA formation, indicating that coagulation occurs by different pathways, depending upon the type of coagulant used. In particular, significant changes in the reactivities of the hydrophilic acidic and non-acidic fractions were observed.

Response surface methodology investigation into the interactions between arsenic and humic acid in water during the coagulation process.

Interactions between arsenic and natural organic matter (NOM) are key limiting factors during the optimisation of drinking water treatment when significant amounts of both must be removed. This work uses Response Surface Methodology (RSM) to investigate how they interact during their simultaneous removal by iron chloride coagulation, using humic acid (HA) as a model NOM substance. Using a three factor Box-Behnken experimental design, As and HA removals were modelled, as well as a combined removal response. ANOVA results showed the significance of the coagulant dose for all three responses. At high initial arsenic concentrations (200μg/l), As removal was significantly hindered by the presence of HA. In contrast, the HA removal response was found to be largely independent of the initial As concentration, with the optimum coagulant dose increasing at increasing HA concentrations. The combined response was similar to the HA removal response, and the interactions evident are most interesting in terms of optimising treatment processes during the preparation of drinking water, highlighting the importance of utilizing RSM for such investigations. The combined response model was successfully validated with two different groundwaters used for drinking water supply in the Republic of Serbia, showing excellent agreement under similar experimental conditions.

Oxidation of natural organic matter with processes involving O3, H2O2 and UV light: formation of oxidation and disinfection by-products

This study investigates the effects of UV photolysis, ozonation and different advanced oxidation processes (O3/UV, H2O2/UV and O3/H2O2/UV) on the oxidation of groundwater natural organic matter (NOM) and by-product formation. Although the investigated treatments only slightly reduce the total organic carbon content (4–15%), the NOM character was changed significantly. The fulvic acid fraction decreased and the content of the hydrophilic acid fraction increased in ozone treated water and even more noticeably in water treated by O3/H2O2/UV. All treatments led to significant increases in polar oxidation by-products such as aldehydes (up to 8 times) and carboxylic acids (up to 34 times), with no clear relationship between the changes in concentrations of these by-products and the addition of H2O2 and the UV dose. Statistical analysis showed a good correlation between carboxylic acids with ozone applications and carboxylic acids and UV254. Trihalomethane and haloacetic acid formation potentials were reduced best (43% for THMFP and 68% for HAAFP) during the O3/H2O2/UV process (0.5 mg O3 per mg DOC; 10 mg H2O2 per L: 600 mL cm−2) using the lower UV dose, and were also well correlated (R = 0.847) during all water treatments. Bromate formation was observed only in the processes involving ozone.

Degradation of Anthraquinone Dye Reactive Blue 4 in Pyrite Ash Catalyzed Fenton Reaction

Pyrite ash (PA) is created by burning pyrite in the chemical production of sulphuric acid. The high concentration of iron oxide, mostly hematite, present in pyrite ash, gives the basis for its application as a source of catalytic iron in a modified Fenton process for anthraquinone dye reactive blue 4 (RB4) degradation. The effect of various operating variables such as catalyst and oxidant concentration, initial pH and RB4 concentration on the abatement of total organic carbon, and dye has been assessed in this study. Here we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions: pH = 2.5; [PA]0 = 0.2 g L−1; [H2O2]0 = 5 mM and initial RB4 concentration up to 100 mg L−1. The pyrite ash Fenton reaction can overcome limitations observed from the classic Fenton reaction, such as the early termination of the Fenton reaction. Metal (Pb, Zn, and Cu) content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metals from the water. These results provide basic knowledge to better understand the modified, heterogeneous Fenton process and apply the PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes.

Correlation of different pollution criteria in the assessment of metal sediment pollution.

In this article an assessment of the sediment metal pollution (cadmium, copper, chromium, lead, nickel, zinc) in the Veliki Backi canal (Serbia) was carried out using pseudo-total metal content, contamination factor (CF), pollution load index (PLI) and enrichment factor (EF). The study also encompassed pore-water metal concentrations and an assessment of sediment pollution based on the analysis of simultaneously extracted metals (SEM), acid volatile sulphides (AVS) and the sequential extraction procedure. The concentrations of metals are likely to result in harmful effects based on the comparison with sediment quality guidelines (Dutch, Canadian, US EPA - United States Environmental Protection Agency). The ratio of simultaneously extracted metals and volatile acid sulphides was found to be greater than 1 in only one location, which is already recognized as a place of high risk based on the criteria applied. Other samples had Σ[SEM]/[AVS] < 1, despite their high risk classification based on the applied criteria. According to the sequential extraction procedure, zinc and nickel exhibit high risk in most samples, whereas other metals show low and medium risk. The CF values for Cr, Cu and Zn were > 6 in most samples, which denotes very high contamination by these metals. The PLI values indicated moderate and high pollution. The EF values for all metals studied except for Cd in some cases were >1.5, suggesting anthropogenic impact. The obtained results will be invaluable for future activities regarding sediment monitoring and will facilitate the selection of appropriate criteria when evaluating sediment quality.

Advanced oxidation processes for the removal of [bmim][Sal] third generation ionic liquids: effect of water matrices and intermediates identification

Unique properties of ionic liquids make them green alternatives for conventional volatile organic compounds. Due to increased production and the high stability of these substances, they could be classified as persistent pollutants and could break through classical treatment systems into natural waters. A preliminary ionic liquid hydrolysis study demonstrated a pH dependent degradation profile with a significant decrease in hydrolysis efficiency as pH lowered from 10.0 to 2.8. In order to examine future prospects for ionic liquid removal, different advanced oxidation processes (TiO2 Degussa P25/H2O2, TiO2 Degussa P25, 7.2Fe/TiO2/H2O2, and H2O2) were studied for their applicability in the degradation of imidazolium-based ionic liquids in aqueous solution. These processes were conducted in the dark as well as in the presence of UVA and simulated sunlight (SS) radiation. Among the investigated dark processes, the 7.2Fe/TiO2/H2O2 system showed the highest efficiency, which can be attributed to a dark heterogeneous Fenton process. Otherwise, the most efficient among all the studied degradation processes was the UVA/TiO2 Degussa P25/H2O2 process. In order to make degradation processes more similar to that of the practical process SS radiation was used. Among studied processes, the 7.2Fe/TiO2/H2O2 system showed the greatest potential for the removal of ionic liquids. Also, it was observed that the impact of anions on the cation degradation efficiency was much more pronounced. Due to the possible fate of ionic liquids in the environment, for five different waters (pond, rain, tap, river, and condensate) degradations in the dark and under simulated sunlight were studied. For all processes, and all water types in the presence of SS radiation a remarkable positive effect of naturally dissolved organic matter on the degradation efficiency was observed. Also, in all experiments, the anion was less stable than the cation. The major photodegradation products identified using liquid chromatography-mass spectrometry (HPLC-MS/MS) techniques were hydroxylated compounds.

Distribution of organic and inorganic substances in the sediments of the “Great Bačka Canal”, a European environmental hotspot

The Great Bačka Canal in Serbia is one of the most polluted waterways in Europe. Surface sediments from the canal were subject to systematic annual monitoring between 2007 and 2014 at 33 representative sampling sites. Eight heavy metals (Ni, Zn, Cd, Cr, Cu, Pb, As and Hg), mineral oils, 16 EPA PAHs and selected pesticides and polychlorinated biphenyls (PCB) were monitored. This study aims to evaluate the quality of the sediments and determine the potential ecological risks in order to establish pollutants of interest. The spatial and temporal influence of different and intense sources of pollution are investigated. The analysis includes multivariate statistical methods (factor analysis of principal component analysis (PCA/FA)) in order to assess the extent and origin (anthropogenic or natural, geogenic sources) of the contaminants detected in the sediment samples and the risks the present to the environment. Various sources, predominantly the food industry, were found to be responsible for most of the contamination by Cd, Cu, Cr and Zn, the mineral oils and PAHs (dibenzo[a,h]anthracene and benzo[a]pyrene contributed 86.0% of the total between 2007 and 2014). In contrast, the As was convincingly of geogenic origin, and the Hg, Pb and Ni present exhibit dual origins. Cd and Cu significantly raise the levels of potential ecological risk at all sampling locations, demonstrating the long-term effects of bioaccumulation and biomagnification. Significantly, the results of this work indicate that Cu, As and dibenzo[a,h]anthracene should be added to the EU watch list of emerging contaminants. This is supported by significant national and similar environmental data from countries in the region.

Sorption Behaviour of Trichlorobenzenes and Polycyclic Aromatic Hydrocarbons in the Absence or Presence of Carbon Nanotubes in the Aquatic Environment

This work investigates the sorption behaviour of six hydrophobic organic compounds (HOCs) from the trichlorobenzenes (TCBs) and polycyclic aromatic hydrocarbons (PAHs) on Danube sediment using batch and column experiments, either in the presence or absence of carbon nanotubes (CNTs). For all HOCs investigated, nonlinear isotherms were obtained. Based on logKoc, it can be concluded that the Danube sediment has a higher sorption affinity for PAHs than TCBs. A positive correlation between HOC molecular hydrophobicity and sorption affinity was obtained, meaning that hydrophobic interactions play a significant role. There was a negative correlation between molecular hydrophobicity and the percentage of eluted HOCs, indicating that more hydrophobic molecules show less mobility in the sediment column. In the presence of CNTs in the sediment column, HOC concentrations in the column eluate decreased by factors of 2–3. Metal oxides and hydroxides on the surface of the sediment under the given experimental conditions had positively charged centres that caused the deposition of CNTs, leading to simultaneous sorption of organic compounds on both sediment organic matter (SOM) and CNTs. The increased retention of HOCs in the presence of CNTs on the sediment column reduces their mobility, which might also suggest that CNTs may be used for remediation of contaminated soils and sediments.

Deployment of Microbial Biosensors to Assess the Performance of Ameliorants in Metal-Contaminated Soils

The remediation of metal-impacted soils requires either the enhanced mobility (and capture) of the target analytes or their effective complexation/immobilisation. In this study, a range of ameliorants (activated carbon, bonemeal, bentonite and CaSx (calcium polysulphide)) were compared to assess their effectiveness in immobilising metals in soils. In addition to chemical analysis (pH and trace element analysis), microbial biosensors were used to assess changes in the water-soluble biotoxicity of metals as a consequence of ameliorant dosing. Management of soil ameliorants requires an enhancement of Kd (solid/solution partition coefficient) if soil leachate is to meet predefined environmental quality standards. Of the ameliorants tested, CaSx was the most effective per unit added for both laboratory-amended and historically contaminated soils, regardless of the metal tested. At the ameliorant concentrations used to effectively immobilise the metals, the biosensor performance was not impaired. Microbial biosensors offered a rapid and relevant screening tool to validate the reduced toxicity associated with the ameliorant dosing and could be calibrated to complement chemical analysis. While laboratory-amended soils were a logical way to evaluate the performance of the ameliorants, they were generally associated with Kd values an order of magnitude lower than those of historically contaminated soils.