Enhanced removal of trace pesticides and alleviation of membrane fouling using hydrophobic-modified inorganic-organic hybrid flocculants in the flocculation-sedimentation-ultrafiltration process for surface water treatment.

Pesticide concentrations in surface water occasionally exceed regulated values due to seasonal events (rainy season in high intensity agricultural areas) or intermittent discharges (leakage, spillage, or other emergency events). The need to remove pesticide compounds in these situations poses a challenge for drinking water treatment plants (DWTPs). In this work, the performance of dosing hydrophobic-modified inorganic-organic hybrid flocculants (HOC-M; lower acute toxicity than corresponding metal salt coagulants; acceptable economic costs when M=Al or Fe; prepared in large-scale quantities), for the removal of four different pesticides (each initial concentration: 0.25 µg/L) from Yangtze River water, and in mitigating membrane fouling, by an integrated flocculation-sedimentation-ultrafiltration (FSUF) process, was evaluated over a period of 40 days; the FSUF is well-established in many DWTPs. The mechanisms underlying the treatment were unveiled by employing a combination of instrumental characterizations, chemical computations, material flow analyses, and statistical analyses. Efficient pesticide removal (80.3%∼94.3%) and membrane fouling reduction (26.6%∼37.3% and 28.3%∼57.6% for reversible and irreversible membrane resistance, respectively) in the FSUF process were achieved by dosing HOC-M, whereas conventional inorganic coagulants were substantially inferior for pesticide removal (< 50%) and displayed more severe fouling development. Hydrophobic association between the pesticides and the hydrophobic organic chain of HOC-M played a predominant role in the improvement in pesticide removal; coexisting particulate/colloid inorganic minerals and natural organic matter with HOC-M adsorbed on the surface, acting as floc building materials, provided sites for the indirect combination of pesticides into flocs. The observed fouling alleviation from dosing HOC-M was ascribed to both the pre-removal of fouling-causing materials in the flocculation-sedimentation prior to UF, and a stable hydrophilization modification effect of residual HOC-M in the UF unit. The latter effect resulted from a hydrophobic association between the PVDF substrate of the membranes and the hydrophobic organic chains of the HOC-M, causing the hydrophilic ends of the HOC-M to be exposed away from the membrane surface, thereby inhibiting foulant accumulation. This work has not only demonstrated the superior performance of dosing HOC-M in the FSUF process for trace pesticide removal in DWTPs, but also clarified the underlying mechanisms.

Tailoring wood waste biochar as a reusable microwave absorbent for pollutant removal: Structure-property-performance relationship and iron-carbon interaction.

This study innovated the concept in designing an efficient and reusable microwave (MW) absorbent through concurrent exploitation of carbon graphitization, oxygen functionalization, and carbothermal iron reduction underpinned by an endothermic co-pyrolysis of wood waste and low-dosage iron. A powerful MW assimilation was accomplished from nanoscale amorphous magnetic particles as well as graphitized microporous carbon-iron skeleton in the biochar composites. Relative to a weak magnetic loss derived from the iron phase, the graphitic carbon architecture with abundant surface functionalities (i.e., CO and CO) exhibited a strong dielectric loss, which was thus prioritized as major active sites during MW reuse. The MW-absorbing biochar demonstrated a fast, robust, and durable removal of a refractory herbicide (2,4-dichlorophenoxy acetic acid) under mild MW irradiation with zero chemical input, low electricity consumption, and negligible Fe dissolution. Overall, this study will foster carbon-neutral industrial wastewater treatment and wood waste valorization.

Multifunctional iron-biochar composites for the removal of potentially toxic elements, inherent cations, and hetero-chloride from hydraulic fracturing wastewater.

This paper evaluates a novel sorbent for the removal of potentially toxic elements, inherent cations, and hetero-chloride from hydraulic fracturing wastewater (FWW). A series of iron-biochar (Fe-BC) composites with different Fe/BC impregnation mass ratios (0.5:1, 1:1, and 2:1) were prepared by mixing forestry wood waste-derived BC powder with an aqueous FeCl3 solution and subsequently pyrolyzing them at 1000 °C in a N2-purged tubular furnace. The porosity, surface morphology, crystalline structure, and interfacial chemical behavior of the Fe-BC composites were characterized, revealing that Fe chelated with CO bonds as COFe moieties on the BC surface, which were subsequently reduced to a CC bond and nanoscale zerovalent Fe (nZVI) during pyrolysis. The performance of the Fe-BC composites was evaluated for simultaneous removal of potentially toxic elements (Cu(II), Cr(VI), Zn(II), and As(V)), inherent cations (K, Na, Ca, Mg, Ba, and Sr), hetero-chloride (1,1,2-trichlorethane (1,1,2-TCA)), and total organic carbon (TOC) from high-salinity (233 g L-1 total dissolved solids (TDS)) model FWW. By elucidating the removal mechanisms of different contaminants, we demonstrated that Fe-BC (1:1) had an optimal reducing/charge-transfer reactivity owing to the homogenous distribution of nZVI with the highest Fe0/Fe2+ ratio. A lower Fe content in Fe-BC (0.5:1) resulted in a rapid exhaustion of Fe0, while a higher Fe content in Fe-BC (2:1) caused severe aggregation and oxidization of Fe0, contributing to its complexation/(co-)precipitation with Fe2+/Fe3+. All of the synthesized Fe-BC composites exhibited a high removal capacity for inherent cations (3.2-7.2 g g-1) in FWW through bridging with the CO bonds and cation-π interactions. Overall, this study illustrated the potential efficacy and mechanistic roles of Fe-BC composites for (pre-)treatment of high-salinity and complex FWW.

Removal of chlorinated organic solvents from hydraulic fracturing wastewater by bare and entrapped nanoscale zero-valent iron.

With the increasing application of hydraulic fracturing, it is urgent to develop an effective and economically feasible method to treat the large volumes of fracturing wastewater. In this study, bare and entrapped nanoscale zero-valent iron (nZVI) were introduced for the removal of carbon tetrachloride (CT) and 1,1,2-trichloroethane (TCA) in model high-salinity fracturing wastewater. With increasing ionic strength (I) from Day-1 (I = 0.35 M) to Day-90 (I = 4.10 M) wastewaters, bare nZVI presented significantly lower removal efficiency of CT (from 53.5% to 38.7%) and 1,1,2-TCA (from 71.1% to 21.7%) and underwent more serious Fe dissolution from 1.31 ±â€¯1.19% in Day-1 to 5.79 ±â€¯0.32% in Day-90 wastewater. Particle aggregation induced by high ionic strength was primarily responsible for the lowered performance of nZVI due to less available reactive sites on nZVI surface. The immobilization of nZVI in alginate with/without polyvinyl alcohol provided resistance to particle aggregation and contributed to the superior performance of entrapped nZVI in Day-90 wastewater for 1,1,2-TCA removal (62.6-72.3%), which also mitigated Fe dissolution (4.00-4.69%). Both adsorption (by polymer matrix) and reduction (by immobilized nZVI) were involved in the 1,1,2-TCA removal by entrapped nZVI. However, after 1-month immersion in synthetic fracturing wastewater, a marked drop in the reactivity of entrapped nZVI for 1,1,2-TCA removal from Day-90 wastewater was observed with significant release of Na and total organic carbon. In summary, bare nZVI was sensitive to the nature of the fracturing wastewater, while the use of environmentally benign entrapped nZVI was more promising for wastewater treatment.

Zero-valent iron for the abatement of arsenate and selenate from flowback water of hydraulic fracturing.

Zero-valent iron (ZVI) was tested for the removal of 150 µg L-1 As(V) and 350 µg L-1 Se(VI) in high-salinity (ionic strength 0.35-4.10 M) flowback water of hydraulic fracturing. Over 90% As(V) and Se(VI) was removed by 2.5 g L-1 ZVI in Day-14 flowback water up to 96-h reaction, with the remaining concentration below the maximum contaminant level for As(V) and criterion continuous concentration for Se(VI) recommended by US EPA. The kinetics of As(V) and Se(VI) removal followed a pseudo-second-order rate expression with the observed rates of 4.51 × 10-2-4.91 × 10-1 and 3.48 × 10-2-6.58 × 10-1 h-1 (with 0.5-10 g L-1 ZVI), respectively. The results showed that Se(VI) removal significantly decreased with increasing ionic strength, while As(V) removal showed little variation. Common competing anions (nitrate, bicarbonate, silicate, and phosphate), present in shallow groundwater and stormwater, caused marginal Se(VI) desorption (2.42 ± 0.13%) and undetectable As(V) desorption from ZVI. The competition between As(V) and Se(VI) for ZVI removal depended on the initial molar ratio and surface sites, which occurred when the Se(VI) concentration was higher than the As(V) concentration in this study. The characterization of As(V)- and Se(VI)-loaded ZVI by X-ray diffraction and Raman analysis revealed that ZVI gradually converted to magnetite/maghemite corrosion products with lepidocrocite in flowback water over 30 days. Similar corrosion compositions were confirmed in aerobic and anaerobic conditions regardless of the molar ratio of As(V) to Se(VI). The high reactivity and stability of ZVI showed its suitability for in-situ prevention of As(V) and Se(VI) migration due to accidental leakage, spillage, or overflow of flowback water.

Potential impact of flowback water from hydraulic fracturing on agricultural soil quality: Metal/metalloid bioaccessibility, Microtox bioassay, and enzyme activities.

Hydraulic fracturing has advanced the development of shale gas extraction, while inadvertent spills of flowback water may pose a risk to the surrounding environment due to its high salt content, metals/metalloids (As, Se, Fe and Sr), and organic additives. This study investigated the potential impact of flowback water on four representative soils from shale gas regions in Northeast China using synthetic flowback solutions. The compositions of the solutions were representative of flowback water arising at different stages after fracturing well establishment. The effects of solution composition of flowback water on soil ecosystem were assessed in terms of metal mobility and bioaccessibility, as well as biological endpoints using Microtox bioassay (Vibrio fischeri) and enzyme activity tests. After one-month artificial aging of the soils with various flowback solutions, the mobility and bioaccessibility of As(V) and Se(VI) decreased as the ionic strength of the flowback solutions increased. The results inferred a stronger binding affinity of As(V) and Se(VI) with the soils. Nevertheless, the soil toxicity to Vibrio fischeri only presented a moderate increase after aging, while dehydrogenase and phosphomonoesterase activities were significantly suppressed with increasing ionic strength of flowback solutions. On the contrary, polyacrylamide in the flowback solutions led to higher dehydrogenase activity. These results indicated that soil enzyme activities were sensitive to the composition of flowback solutions. A preliminary human health risk assessment related to As(V) suggested a low level of cancer risk through exposure via ingestion, while holistic assessment of environmental implications is required.

Low pressure UV/H2O2 treatment for the degradation of the pesticides metaldehyde, clopyralid and mecoprop - Kinetics and reaction product formation.

The degradation kinetics of three pesticides - metaldehyde, clopyralid and mecoprop - by ultraviolet photolysis and hydroxyl radical oxidation by low pressure ultraviolet hydrogen peroxide (LP-UV/H2O2) advanced oxidation was determined. Mecoprop was susceptible to both LP-UV photolysis and hydroxyl radical oxidation, and exhibited the fastest degradation kinetics, achieving 99.6% (2.4-log) degradation with a UV fluence of 800 mJ/cm(2) and 5 mg/L hydrogen peroxide. Metaldehyde was poorly degraded by LP-UV photolysis while 97.7% (1.6-log) degradation was achieved with LP-UV/H2O2 treatment at the maximum tested UV fluence of 1000 mJ/cm(2) and 15 mg/L hydrogen peroxide. Clopyralid was hardly susceptible to LP-UV photolysis and exhibited the lowest degradation by LP-UV/H2O2 among the three pesticides. The second-order reaction rate constants for the reactions between the pesticides and OH-radicals were calculated applying a kinetic model for LP-UV/H2O2 treatment to be 3.6 × 10(8), 2.0 × 10(8) and 1.1 × 10(9) M(-1) s(-1) for metaldehyde, clopyralid and mecoprop, respectively. The main LP-UV photolysis reaction product from mecoprop was 2-(4-hydroxy-2-methylphenoxy) propanoic acid, while photo-oxidation by LP-UV/H2O2 treatment formed several oxidation products. The photo-oxidation of clopyralid involved either hydroxylation or dechlorination of the ring, while metaldehyde underwent hydroxylation and produced acetic acid as a major end product. Based on the findings, degradation pathways for the three pesticides by LP-UV/H2O2 treatment were proposed.

Humic acid aggregation in zero-valent iron systems and its effects on trichloroethylene removal.

The influence of natural organic matter on contaminant removal by Fe(0) systems has been of increasing concern. Recent studies have shown that, in addition to direct sorption on the Fe(0) surfaces, humic acid complexation with dissolved iron released from corrosion results in the formation of colloids and aggregates in solution that may affect contaminant removal. High-pressure size-exclusion chromatographic analyses revealed increasing molecular weights of dissolved humic acids with reaction time. Humic acid aggregation occurred across a wide range of molecular weight fractions. Fourier transform infrared spectroscopic analysis of humic acid aggregates suggested the presence of inner-sphere complexation involving different oxygen-containing functional groups; hydrophobic interactions also probably contributed to aggregation as the humic acid of more aromatic and hydrophobic character was aggregated at a faster rate. Because of multiple underlying processes, a variety of cross-correlated physicochemical properties of humic acids contributed to their aggregation. The presence of humic acid aggregates provided an additional hydrophobic domain for partitioning that enhanced trichloroethylene removal, although steric blocking of the Fe(0) surfaces may inhibit its reduction to some extent. Comparable effects were demonstrated for various types of humic acids.

The aqueous degradation of butylated hydroxyanisole by UV/S2O8(2-): study of reaction mechanisms via dimerization and mineralization.

Three distinctive phases of BHA reactivity toward UV/ S2O8(2-) at acidic, neutral, and basic pH range were examined, where 80-100% mineralization has been observed within an hour of irradiation under 254 nm. A reduction in solution pH during the reaction was observed mainly due to the complete conversion of S2O8(2-) to sulfate ion together with proton generation. Seven measurable intermediates were found via an oxidation and dimerization process at all tested pH levels. The BHA decay mechanisms are quite different in acidic condition and at other pH levels. There are three unique intermediates that are only detectable at pH 3 via two additional pathways. This is due to the generation of weaker oxidants or radicals which results in a slower degradation of the BHA, and therefore, the accumulation of these intermediates to detectable levels. The rate of BHA decay generally increases from low to high pH levels; however, the corresponding mineralization at higher pH is retarded due to the futile process of recombining radicals and involvement of intermediates. Therefore, neutral pH was suggested to be the optimum condition in terms of mineralization and moderate efficiency in removing BHA.