Microplastics in ecosystems: Critical review of occurrence, distribution, toxicity, fate, transport, and advances in experimental and computational studies in surface and subsurface water.

Microplastics (MPs), particles under 5 mm, pervade water, soil, sediment, and air due to increased plastic production and improper disposal, posing global environmental and health risks. Examining their distribution, quantities, fate, and transport is crucial for effective management. Several studies have explored MPs' sources, distribution, transport, and biological impacts, primarily focusing on the marine environment. However, there is a need for a comprehensive review of all environmental systems together for enhanced pollution control. This review critically examines the occurrence, distribution, fate, and transport of MPs in the following environments: freshwater, marine, and terrestrial ecosystems. The concentration of MPs is highly variable in the environment, ranging from negligible to significant amounts (0.003-519.223 items/liter in water and 0-18,000 items/kg dry weight sediment, respectively). Predominantly, these MPs manifest as fibers and fragments, with primary polymer types including polypropylene, polystyrene, polyethylene, and polyethylene terephthalate. A complex interplay of natural and anthropogenic actions, including wastewater treatment plant discharges, precipitation, stormwater runoff, inadequate plastic waste management, and biosolid applications, influences MPs' presence and distribution. Our critical synthesis of existing literature underscores the significance of factors such as wind, water flow rates, settling velocities, wave characteristics, plastic morphology, density, and size in determining MPs' transport dynamics in surface and subsurface waters. Furthermore, this review identifies research gaps, both in experimental and simulation, and outlines pivotal avenues for future exploration in the realm of MPs.

Leaching characteristics of nutrients in food waste digestate-derived biochar.

Food waste anaerobic digestion requires proper utilization of solid digestate, and pyrolysis emerges as an effective method to produce nutrient-rich biochar. This study investigated the leaching characteristics and speciation changes of nutrients in food waste digestate (FWD)-derived biochar pyrolyzed at 350 °C (BC350), 450 °C (BC450), and 550 °C (BC550). BC350 featured inorganic nitrogen, while BC450 and BC550 contained elevated organic nitrogen. Nitrogen, potassium, and dissolved organic carbon were released via a quick surface wash-off process. Polyphosphates prevailed in BC350 and leached through a fast diffusion-controlled process. BC450 and BC550 were dominated by Ca/Mg orthophosphates and released via a slow dissolution-controlled process. Leachates from BC450 and BC550 stimulated the shoot length of wheat seeds. After 5 leaching cycles, there were more aromatic dissolved organics, and BC450 and BC550 exhibited higher abundance of C-N and O-P-O. Overall, pyrolysis of FWD at 450 °C and 550 °C shows potential in producing slow-release biochar fertilizers for resource recycling.

Airborne Pesticides-Deep Diving into Sampling and Analysis.

The escalating utilization of pesticides has led to pronounced environmental contamination, posing a significant threat to agroecosystems. The extensive and persistent global application of these chemicals has been linked to a spectrum of acute and chronic human health concerns. This review paper focuses on the concentrations of airborne pesticides in both indoor and outdoor environments. The collection of diverse pesticide compounds from the atmosphere is examined, with a particular emphasis on active and passive air sampling techniques. Furthermore, a critical evaluation is conducted on the methodologies employed for the extraction and subsequent quantification of airborne pesticides. This analysis takes into consideration the complexities involved in ensuring accurate measurements, highlighting the advancements and limitations of current practices. By synthesizing these aspects, this review aims to foster a more comprehensive and informed comprehension of the intricate dynamics related to the presence and measurement of airborne pesticides. This, in turn, is poised to significantly contribute to the refinement of environmental monitoring strategies and the augmentation of precise risk assessments.

Airborne Pesticides from Agricultural Practices: A Critical Review of Pathways, Influencing Factors, and Human Health Implications.

This critical review examines the release of pesticides from agricultural practices into the air, with a focus on volatilization, and the factors influencing their dispersion. The review delves into the effects of airborne pesticides on human health and their contribution to anthropogenic air pollution. It highlights the necessity of interdisciplinary research encompassing science, technology, public policy, and agricultural practices to effectively mitigate the risks associated with pesticide volatilization and spray dispersion. The text acknowledges the need for more research to understand the fate and transport of airborne pesticides, develop innovative application technologies, improve predictive modeling and risk assessment, and adopt sustainable pest management strategies. Robust policies and regulations, supported by education, training, research, and development, are crucial to ensuring the safe and sustainable use of pesticides for human health and the environment. By providing valuable insights, this review aids researchers and practitioners in devising effective and sustainable solutions for safeguarding human health and the environment from the hazards of airborne pesticides.

Reactivity characterization of SiO2-coated nano zero-valent iron for iodoacetamide degradation: The effects of SiO2 thickness, and the roles of dehalogenation, hydrolysis and adsorption.

The effect of SiO2-layer thickness in SiO2-coated nano zero-valent iron (nZVI) particles on the reactivity characteristics of iodoacetamide (IAcAm) degradation was evaluated. SiO2-layer thicknesses ranging from 3.6 to 27.3 nm were obtained through varying tetraethyl orthosilicate dosages of 0.001-1 M. The crystallinity, surface chemical composition, and physicochemical properties were evaluated for their effects on synergetic degradation mechanisms, dehalogenation, hydrolysis, and adsorption. At a thickness of 3.6 nm, the SiO2 layer offered the highest observed pseudo-first-order rate (kobs) and higher rates of IAcAm degradation were maintained under pH fluctuations (pH 5-7) and aerobic conditions compared to pristine nZVI. At this SiO2-layer thickness (3.6 nm), the rate of iron oxide-layer formation was reduced and the migration of reactive iron species (Fe0 and Fe2+) for the dehalogenation and hydrolysis reactions was enabled. In a single-solute solution, IAcAm elimination was greater than bromoacetamide and chloroacetamide elimination due to the weak ionic I-C bond. In mixed solute conditions, the hydrophobicity of chloroacetamide played a more significant role in competitive degradation through greater adsorption. The proportion of dehalogenation relative to hydrolysis during IAcAm degradation by pristine nZVI and SiO2-coated nZVI was approximately 0.6:0.4. Iodoacetic acid and acetic acid were detected as intermediates in the degradation pathway of IAcAm by pristine nZVI. In contrast, the SiO2 layer on nZVI can accelerate the transformation of IAcAm to acetamide and iodoacetic acid. The electrolyte background of tap water exhibited a slight inhibitory effect on the degradation of IAcAm for both nZVI and SiO2-coated nZVI.

Trihalomethanes in Water Supply System and Water Distribution Networks.

The formation of trihalomethanes (THMs) in natural and treated water from water supply systems is an urgent research area due to the carcinogenic risk they pose. Seasonal effects and pH have captured interest as potential factors affecting THM formation in the water supply and distribution systems. We investigated THM occurrence in the water supply chain, including raw and treated water from water treatment plants (coagulation, sedimentation, sand filtration, ClO2-disinfection processes, and distribution pipelines) in the Chiang Mai municipality, particularly the educational institute area. The effects of two seasons, rainy (September-November 2019) and dry (December 2019-February 2020), acted as surrogates for the water quality profile and THM occurrence. The results showed that humic acid was the main aromatic and organic compound in all the water samples. In the raw water sample, we found a correlation between surrogate organic compounds, including SUVA and dissolved organic carbon (DOC) (R2 = 0.9878). Four species of THMs were detected, including chloroform, bromodichloromethane, dibromochloromethane, and bromoform. Chloroform was the dominant species among the THMs. The highest concentration of total THMs was 189.52 µg/L. The concentration of THMs tended to increase after chlorination when chlorine dioxide and organic compounds reacted in water. The effect of pH on the formation of TTHMs was also indicated during the study. TTHM concentrations trended lower with a pH ≤ 7 than with a pH ≥ 8 during the sampling periods. Finally, in terms of health concerns, the concentration of TTHMs was considered safe for consumption because it was below the standard (<1.0) of WHO's Guideline Values (GVs).

Iron turning waste: Low cost and sustainable permeable reactive barrier media for remediating dieldrin, endrin, DDT and lindane in groundwater.

The feasibility and effectiveness of iron turning waste as low cost and sustainable permeable reactive barrier (PRB) media for remediating dieldrin, endrin, dichlorodiphenyltrichloroethane (DDT), and lindane individually (batch system) and combined (continuous flow column) in water were investigated. After 10 min of reaction in a batch system, removal of endrin, dieldrin, and DDT was higher (86-91 %) than lindane (41 %) using 1 g of iron turning waste in 200 mL of pesticide solution (20 µg/L for each pesticide). Among the studied pesticides, only lindane removal decreased substantially in the presence of nitrate (37 %) and magnesium (18 %). Acidic water environment (pH = 4) favored the pesticide removal than neutral and basic environments. For the column experiments, sand alone as PRB media was ineffective for remediating the pesticides in water. When only iron turning was used, the removal efficiencies of lindane, endrin, and dieldrin were 83-88 % and remained stable during 60 min of the experiments. DDT removal was less than other pesticides (58 %). Sandwiching the iron turning waste media between two sand layers improved DDT removal (79 %) as well as limited the iron content below a permissible level in product water. In a long-term PRB column performance evaluation, iron turning waste (150 g) removed all pesticides in water (initial concentration of each pesticide = 2 µg/L) effectively (≥94 %) at a hydraulic retention time of 1.6 h. Iron turning waste, which was mainly in the form of zerovalent iron (Fe0), was oxidized to ferrous (Fe2+) and ferric (Fe3+) iron during its reaction with pesticides, and electrons donated by Fe0 and Fe2+ were responsible for complete dechlorination of all the pesticides. Therefore, it can be used as inexpensive and sustainable PRB media for groundwater remediation especially in developing countries where groundwater contamination with pesticides is more prevalent.

Interactions between natural organic matter fractions and nanoscale zero-valent iron.

The presence of natural organic matter (NOM) in groundwater could play an important role in the removal of contaminants by nanoscale zero-valent iron (NZVI). NOM has a heterogeneous structure and can be divided into 6 fractions based on polarity and charges: hydrophobic acid (HPOA), hydrophobic base (HPOB), hydrophobic neutral (HPON), hydrophilic acid (HPIA), hydrophilic base (HPIB), and hydrophilic neutral (HPIN). The objective of this study was to evaluate the interactions between NOM fractions and NZVI using two approaches: 1) the interaction between NOM fraction isolates and NZVI and 2) bulk NOM fractionation before and after reaction with NZVI. Two sources of NOM-groundwater (GWNOM), Khon Kaen, Thailand and Suwannee River NOM (SRNOM), USA-were examined. The isolated NOM had more interactions with NZVI at pH 5 compared to pH 7 and 9 for both GWNOM and SRNOM. HPOA of GWNOM had the highest adsorption capacity (qe) of 6.95 mg/g (pH 5), and that was also the case for HPIA of SRNOM (18.66 mg/g, pH 5). HPIN of both GWNOM and SRNOM yielded the lowest qe among the six fractions. The adsorption capacities of NOM fractions were well correlated with specific ultraviolet absorbance. Fluorescence excitation-emission spectra revealed that protein-like components preferentially reacted with NZVI. The results of bulk NOM fractionation after reacting with NZVI indicated that NOM not only adsorbed on NZVI but also reacted with NZVI and transformed to become more hydrophilic and neutral. This study's findings suggest that different NOM fractions had varying interactions with NZVI. The acid fractions tended to interact more than the other fractions. This work provides a deeper understanding of the reactivity between NOM and NZVI.

Photolytic fate of (E)- and (Z)-endoxifen in water and treated wastewater exposed to sunlight.

Endoxifen is the main active metabolite of a common cytostatic drug, tamoxifen. Endoxifen has been recently detected in the final effluent of municipal wastewater treatment plants. The antiestrogenic activity of endoxifen could bring negative effects to aquatic life if released to the water environment. This study elucidated the fate and susceptibility of (E)- and (Z)-endoxifen (2 µg mL-1, 1:1 wt ratio between the two easily interchangeable isomers) in wastewater and receiving surface water to sunlight. Phototransformation by-products (PBPs) and their toxicity were determined. Sunlight reduced at least 83% of endoxifen concentration in wastewater samples, whereas in surface water samples, 60% of endoxifen was photodegraded after 180 min of the irradiation. In ultrapure water samples spiked with endoxifen, PBPs were mainly generated via con-rotatory 6π-photocyclization, followed by oxidative aromatization. These PBPs underwent secondary reactions leading to a series of PBPs with different molecular weights. Eight PBPs were identified and the toxicity analysis via the Toxicity Estimation Software Tool revealed that seven of these PBPs are more toxic than endoxifen itself. This is likely due to the formation of poly-aromatic core in the PBPs due to exposure to sunlight. Therefore, highly toxic PBPs may be generated if endoxifen is present in water and wastewater exposed to sunlight. The presence, fates and activities of these PBPs in surface water especially at locations close to treated wastewater discharge points should be investigated.

Virgin (Fe0) and microbially regenerated (Fe2+) iron turning waste for treating chlorinated pesticides in water.

This work investigated the applicability of iron turning waste as filtration media for treating mixture of organochlorine pesticides (OCPs) in water and the ability of non-pathogenic bacterium Shewanella oneidensis to regenerate the exhausted iron turning waste for reuse. In batch experiments, 1.5 × 104 mg/L of iron turning waste efficiently removed (≥85%) five out of six pesticides in 200 mL of water (20 µg/L for each pesticide) in 10 min. Increasing the iron dose from 2.5 × 103 to 1.5 × 104 mg/L enhanced the removal of heptachlor, endosulfan, dieldrin, and endrin by 5.7, 13.2, 23.3, and 39.4%, respectively, whereas lindane and dichlorodiphenyltrichloroethane removal was comparable when using 2.5 × 103 and 1.5 × 104 mg/L of iron. Better pesticide removal (except lindane) was achieved when the initial concentration of each pesticide was higher (20 µg/L versus 1 µg/L) in the solution. Acidic pH favored OCPs (except endosulfan) removal. S. oneidensis efficiently reduced 80 ± 5% of dissolved ferric iron (Fe3+) to ferrous iron (Fe2+) in 72 h. Microbially regenerated Fe2+ iron removed all six OCPs in water efficiently (52-91%) and at similar levels as provided by virgin iron turning (38-100%). Lindane, endosulfan, and dieldrin removal increased 4-fold using S. oneidensis regenerated iron compared to exhausted iron.

Iron turning waste media for treating Endosulfan and Heptachlor contaminated water.

This study explored the application of iron turning waste for the degradation of heptachlor and endosulfan. In batch experiments, 2.5 g of iron turning waste efficiently removed 96% of heptachlor and 85% of endosulfan in 200 mL of water (20 µg/L for each pesticide) in ten minutes. By increasing the iron turning dose from 1 g to 2.5 g, pseudo second order removal rates of heptachlor and endosulfan increased 1.5-fold and 1.37-fold, respectively. Among the minerals in groundwater, calcium and potassium lowered heptachlor removal (8-10%), whereas their effect on endosulfan removal was minimal. Endosulfan removal increased 16%, when water pH was raised from 4 to 10. The effect of water pH on heptachlor removal was minimal. The removal of heptachlor and endosulfan dropped to 55% and 46%, respectively, when the initial concentration was 1 µg/L. In a continuous flow system, iron turning worked better in combination with sand media. Water flow rate (5-15 mL/min) had a limited effect on the removal of both pesticides (initial concentration of 2 µg/L) which increased with increasing iron turning dose (100-150 g) for endosulfan. Heptachlor removal remained stable (100%) regardless of the iron turning amount (100-150 g) used in a filtration column. Iron turning based filter completely removed heptachlor throughout the filtration period (600 h), whereas endosulfan removal dropped from 100% to 88-90% after 300 h. Endosulfan and heptachlor were degraded into nonanal and heptanal, respectively. Iron turning waste was characterized using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) before and after its reactions with both pesticides. XRD and XPS analyses revealed that virgin iron turning waste consisted of zerovalent iron (Fe0) and iron oxides, and Fe0 was transformed to magnetite (Fe3O4) after reacting with both pesticides. Based on detected degradation by-products, the removal mechanism and degradation pathways for both pesticides were elucidated.

Simultaneous bioprecipitation of cadmium to cadmium sulfide nanoparticles and nitrogen fixation by Rhodopseudomonas palustris TN110.

This study investigated the abilities of a purple non-sulfur bacterium, Rhodopseudomonas palustris TN110 to bioremediate cadmium through the biosynthesis of CdS nanoparticles and to fix nitrogen simultaneously. Under microaerobic-light conditions, R. palustris TN110 synthesized CdS nanoparticles. The produced CdS nanoparticles had a spherical shape and an average size of 4.85 nm. The Fourier transform infrared spectrum of the nanoparticles reveals the carbonyl groups, bending vibrations of the amide I and II bands of proteins, and CN stretching vibrations of aromatic and aliphatic amines. These bands and groups suggest protein capping/binding on the surface of the nanoparticles. R. palustris TN110 converted 25.61% of 0.2 mM CdCl2 to CdS nanoparticles under optimal conditions (pH 7.5, 30 °C and 3000 lux). The half maximal inhibitory concentration (IC50) value of the produced CdS nanoparticles was 1.76 mM. The produced CdS nanoparticles at IC50 up-regulated two genes associated with nitrogen fixation: Mo-Fe nitrogenase gene (nifH) and V-Fe nitrogenase gene (vnfG) at 2.83 and 2.27 fold changes, respectively. On the contrary, the produced CdS nanoparticles slightly down-regulated Fe-Fe nitrogenase gene (anfG). The amounts of ammonia released by the strain support the gene expression results. R. palustris TN110 has great potential to serve concurrently as a cadmium bioremediation agent and a nitrogen fixer. The strain could be beneficial to paddy fields that are contaminated with Cd through run off from mining and chemical fertilizer applications.

Photolysis of glutaraldehyde in brine: A showcase study for removal of a common biocide in oil and gas produced water.

Glutaraldehyde (GA) has been used extensively as a biocide in hydraulic fracturing fluid leading to its presence in oil and gas produced water. In this study, photolysis was used to degrade GA from brine solutions simulating produced water. Photolysis of GA was performed under ultraviolet (UV) irradiation. GA can be photolyzed by UV at all studied conditions with the efficiency ranging from 52 to 85% within one hour irradiation. Photolysis of GA followed pseudo-first order kinetics. A photolysis rate constant of GA at 0.1 mM in 200 g/L of salt at pH 7 was 0.0269 min-1 with a quantum yield of 0.0549 under 224 W illumination. The degradation rate of GA increased with increasing incident light intensity and decreasing pH. Increasing initial GA concentration resulted in decreasing degradation rate of GA. The degradation of GA was affected by salt concentration. At lower salt concentrations, notable retardation of GA photodegradation rate was observed while at higher salt concentrations GA photodegradation was improved compared to those without salt. OH was more dominant in sample without salt than sample with salt suggesting different photolytic mechanisms, indirect and direct photolysis, respectively. Oligomers were identified as the main photoproducts of GA photolysis.

Risk assessment of human exposure to Ra-226 in oil produced water from the Bakken Shale.

Unconventional oil production in North Dakota (ND) and other states in the United States uses large amounts of water for hydraulic fracturing to stimulate oil flow. Most of the water used returns to the surface as produced water (PW) containing different constituents. Some of these contents are total dissolved solids and radionuclides. The most predominant radionuclide in PW is radium-226 (Ra-226) of which level depends on several factors including the content of certain cations. A multivariate regression model was developed to predict Ra-226 in PW from the Bakken Shale based on the levels of barium, strontium, and calcium. The simulated Ra-226 activity concentration in PW was 535 pCi/L supporting extremely limited actual data based on three PW samples from the Bakken (527, 816, and 1210 pCi/L). The simulated activity concentration was further analyzed by studying its impact in the event of a PW spill reaching a surface water body that provides drinking water, irrigation water for crops, and recreational fishing. Using food transfer factors found in the literature, the final annual effective dose rate for an adult in ND was estimated. The global average annual effective dose rate via food and drinking water is 0.30 mSv, while the predicted dose rate in this study was 0.49 mSv indicating that there is potential risk to human health in ND due to Ra-226 in PW spills. This predicted dose rate is considered the best case scenario as it is based on the simulated Ra-226 activity concentration in PW of 535 pCi/L which is close to the low end actual activity concentration of 527 pCi/L.

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.

Aging effects on chemical transformation and metal(loid) removal by entrapped nanoscale zero-valent iron for hydraulic fracturing wastewater treatment.

In this study, alginate and polyvinyl alcohol (PVA)-alginate entrapped nanoscale zero-valent iron (nZVI) was tested for structural evolution, chemical transformation, and metals/metalloids removal (Cu(II), Cr(VI), Zn(II), and As(V)) after 1-2month passivation in model saline wastewaters from hydraulic fracturing. X-ray diffraction analysis confirmed successful prevention of Fe0 corrosion by polymeric entrapment. Increasing ionic strength (I) from 0 to 4.10M (deionized water to Day-90 fracturing wastewater (FWW)) with prolonged aging time induced chemical instability of alginate due to dissociation of carboxyl groups and competition for hydrogen bonding with nZVI, which caused high Na (7.17%) and total organic carbon (24.6%) dissolution from PVA-alginate entrapped nZVI after 2-month immersion in Day-90 FWW. Compared to freshly-made beads, 2-month aging of PVA-alginate entrapped nZVI in Day-90 FWW promoted Cu(II) and Cr(VI) uptake in terms of the highest removal efficiency (84.2% and 70.8%), pseudo-second-order surface area-normalized rate coefficient ksa (2.09×10-1Lm-2h-1 and 1.84×10-1Lm-2h-1), and Fe dissolution after 8-h reaction (13.9% and 8.45%). However, the same conditions inhibited Zn(II) and As(V) sequestration in terms of the lowest removal efficiency (31.2% and 39.8%) by PVA-alginate nZVI and ksa (4.74×10-2Lm-2h-1 and 6.15×10-2Lm-2h-1) by alginate nZVI. The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in metals/metalloids removal by entrapped nZVI after aging was attributed to distinctive removal mechanisms: (i) enhanced Cu(II) and Cr(VI) removal by nZVI reduction with accelerated electron transfer after pronounced dissolution of non-conductive polymeric immobilization matrix; (ii) suppressed Zn(II) and As(V) removal by nZVI adsorption due to restrained mass transfer after blockage of surface-active micropores. Entrapped nZVI was chemically fragile and should be properly stored and regularly replaced for good performance.

Membrane Alterations in Pseudomonas putida F1 Exposed to Nanoscale Zerovalent Iron: Effects of Short-Term and Repetitive nZVI Exposure.

In this study, we report the effect of the commercial nanoscale zerovalent iron (nZVI) on environmental bacteria, emphasizing the importance of nZVI-bacterial membrane interaction on nZVI toxicity as well as the adaptability of bacteria to nZVI. Exposure of Pseudomonas putida F1 to 0.1, 1.0, and 5.0 g/L of nZVI caused the reduction in colony forming units (CFUs) substantially for almost 3 orders of magnitude. However, a rebound in the cell number was observed after the prolonged exposure except for 5.0 g/L nZVI at which bacterial viability was completely inhibited. Upon exposure, nZVI accumulated on and penetrated into the bacterial cell membrane. Cell membrane composition analysis revealed the conversion of the cis to trans isomer of unsaturated fatty acid upon short-term nZVI exposure, resulting in a more rigid membrane counteracting the membrane-fluidizing effect of nZVI. Several cycles of repetitive exposure of cells to 0.1 g/L nZVI induced a persistent phenotype of P. putida F1 as indicated by smaller colony morphology, a more rigid membrane, and higher tolerance to nZVI. A low interaction between nZVI particles and the surface of the nZVI-persistent phenotypic cells reduced the nZVI-induced membrane damage. This study unveils the significance of nZVI-membrane interaction on toxicity of nZVI toward bacteria.

Nanoscale zero-valent iron for metal/metalloid removal from model hydraulic fracturing wastewater.

Nanoscale zero-valent iron (nZVI) was tested for the removal of Cu(II), Zn(II), Cr(VI), and As(V) in model saline wastewaters from hydraulic fracturing. Increasing ionic strength (I) from 0.35 to 4.10 M (Day-1 to Day-90 wastewaters) increased Cu(II) removal (25.4-80.0%), inhibited Zn(II) removal (58.7-42.9%), slightly increased and then reduced Cr(VI) removal (65.7-44.1%), and almost unaffected As(V) removal (66.7-75.1%) by 8-h reaction with nZVI at 1-2 g L-1. The removal kinetics conformed to pseudo-second-order model, and increasing I decreased the surface area-normalized rate coefficient (ksa) of Cu(II) and Cr(VI), probably because agglomeration of nZVI in saline wastewaters restricted diffusion of metal(loid)s to active surface sites. Increasing I induced severe Fe dissolution from 0.37 to 0.77% in DIW to 4.87-13.0% in Day-90 wastewater; and Fe dissolution showed a significant positive correlation with Cu(II) removal. With surface stabilization by alginate and polyvinyl alcohol, the performance of entrapped nZVI in Day-90 wastewater was improved for Zn(II) and Cr(VI), and Fe dissolution was restrained (3.20-7.36%). The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in removal trends from Day-1 to Day-90 wastewaters was attributed to: (i) distinctive removal mechanisms of Cu(II) and Cr(VI) (adsorption, (co-)precipitation, and reduction), compared to Zn(II) (adsorption) and As(V) (bidentate inner-sphere complexation); and (ii) changes in solution speciation (e.g., from Zn2+ to ZnCl3- and ZnCl42-; from CrO42- to CaCrO4 complex). Bare nZVI was susceptible to variations in wastewater chemistry while entrapped nZVI was more stable and environmentally benign, which could be used to remove metals/metalloids before subsequent treatment for reuse/disposal.

Characterizations of purple non-sulfur bacteria isolated from paddy fields, and identification of strains with potential for plant growth-promotion, greenhouse gas mitigation and heavy metal bioremediation.

This study was aimed at selecting purple non-sulfur bacteria (PNSB) isolated from various paddy fields, including Cd- and Zn-contaminated paddy fields, based on their biofertilizer properties. Among 235 PNSB isolates, strain TN110 was most effective in plant growth-promoting substance (PGPS) production, releasing 3.2 mg/L of [Formula: see text] , 4.11 mg/L of 5-aminolevulinic acid (ALA) and 3.62 mg/L of indole-3-acetic acid (IAA), and reducing methane emission up to 80%. This strain had nifH, vnfG and anfG, which are the Mo, V and Fe nitrogenase genes encoded for key enzymes in nitrogen fixation under different conditions. This strain provided 84% and 55% removal of Cd and Zn, respectively. Another isolate, TN414, not only produced PGPS (1.30 mg/L of [Formula: see text] , 0.94 mg/L of ALA and 0.65 mg/L of IAA), but was also efficient in removing both Cd and Zn at 72% and 74%, respectively. Based on 16S rDNA sequencing, strain TN110 was identified as Rhodopseudomonas palustris, while strain TN414 was Rubrivivax gelatinosus. A combination of TN110 and TN414 could potentially provide a biofertilizer, which is a greener alternative to commercial/chemical fertilizers and an agent for bioremediation of heavy metals and greenhouse gas mitigation in paddy fields.

Holistic risk assessment of surface water contamination due to Pb-210 in oil produced water from the Bakken Shale.

A holistic risk assessment of surface water (SW) contamination due to lead-210 (Pb-210) in oil produced water (PW) from the Bakken Shale in North Dakota (ND) was conducted. Pb-210 is a relatively long-lived radionuclide and very mobile in water. Because of limited data on Pb-210, a simulation model was developed to determine its concentration based on its parent radium-226 and historical total dissolved solids levels in PW. Scenarios where PW spills could reach SW were analyzed by applying the four steps of the risk assessment process. These scenarios are: (1) storage tank overflow, (2) leakage in equipment, and (3) spills related to trucks used to transport PW. Furthermore, a survey was conducted in ND to quantify the risk perception of PW from different stakeholders. Findings from the study include a low probability of a PW spill reaching SW and simulated concentration of Pb-210 in drinking water higher than the recommended value established by the World Health Organization. Also, after including the results from the risk perception survey, the assessment indicates that the risk of contamination of the three scenarios evaluated is between medium-high to high.