A biological and chemical approach to restoring water quality: A case study in an urban eutrophic pond

Efforts to improve water quality of eutrophic ponds often involve implementing changes to watershed management practices to reduce external nutrient loads. While this is required for long-term recovery and prevention, eutrophic conditions are often sustained through the recycling of internal nutrients already present within the waterbody. In particular, internal phosphorus bound to organic material and adsorbed to sediment has the potential to delay lake recovery for decades. Thus, pond and watershed management techniques are needed that not only reduce external nutrient loading but also mitigate the effects of internal nutrients already present. Therefore, our objective was to demonstrate a biological and chemical approach to remove and sequester nutrients present and entering an urban retention pond. A novel biological and chemical management technique was designed by constructing a 37 m2 (6.1 m × 6.1 m) floating treatment wetland coupled with a slow-release lanthanum composite inserted inside an airlift pump. The floating treatment wetland promoted microbial denitrification and plant uptake of nitrogen and phosphorus, while the airlift pump slowly released lanthanum to the water column over the growing season to reduce soluble reactive phosphorus. The design was tested at the microcosm and field scales, where nitrate-N and phosphate-P removal from the water column was significant (α = 0.05) at the microcosm scale and observed at the field scale. Two seasons of field sampling showed both nitrate-N and phosphate-P concentrations were reduced from 50 μg L–1 in 2020 to \u3c10 μg L–1 in 2021. Load calculations of incoming nitrate-N and phosphate-P entering the retention pond from the surrounding watershed indicate the presented biological-chemical treatment is sustainable and will minimize the effects of nutrient loading from nonpoint source pollution

Literature Review: Global Neonicotinoid Insecticide Occurrence in Aquatic Environments

Neonicotinoids have been the most commonly used insecticides since the early 1990s. Despite their efficacy in improving crop protection and management, these agrochemicals have gained recent attention for their negative impacts on non-target species such as honeybees and aquatic invertebrates. In recent years, neonicotinoids have been detected in rivers and streams across the world. Determining and predicting the exposure potential of neonicotinoids in surface water requires a thorough understanding of their fate and transport mechanisms. Therefore, our objective was to provide a comprehensive review of neonicotinoids with a focus on their fate and transport mechanisms to and within surface waters and their occurrence in waterways throughout the world. A better understanding of fate and transport mechanisms will enable researchers to accurately predict occurrence and persistence of insecticides entering surface waters and potential exposure to non-target organisms in agricultural intensive regions. This review has direct implications on how neonicotinoids are monitored and degraded in aquatic ecosystems. Further, an improved understanding of the fate and transport of neonicotinoids aide natural resource practitioners in the development and implementation of effective best management practices to reduce the potential impact and exposure of neonicotinoids in waterways and aquatic ecosystems

Using Slow-Release Permanganate Candles to Remove TCE from a Low Permeable Aquifer at a Former Landfill

Past disposal of industrial solvents into unregulated landfills is a significant source of groundwater contamination. In 2009, we began investigating a former unregulated landfill with known trichloroethene (TCE) contamination. Our objective was to pinpoint the location of the plume and treat the TCE using in situ chemical oxidation (ISCO). We accomplished this by using electrical resistivity imaging (ERI) to survey the landfill and map the subsurface lithology. We then used the ERI survey maps to guide direct push groundwater sampling. A TCE plume (100-600 µg L-1) was identified in a low permeable silty-clay aquifer (Kh = 0.5 m d-1) that was within 6 m of ground surface. To treat the TCE, we manufactured slow-release potassium permanganate candles (SRPCs) that were 91.4 cm long and either 5.1 cm or 7.6 cm in dia. For comparison, we inserted equal masses of SRPCs (7.6-cm vs 5.1-cm dia) into the low permeable aquifer in staggered rows that intersected the TCE plume. The 5.1-cm dia candles were inserted using direct push rods while the 7.6-cm SRPCs were placed in 10 permanent wells. Pneumatic circulators that emitted small air bubbles were placed below the 7.6-cm SRPCs in the second year. Results 15 months after installation showed significant TCE reductions in the 7.6-cm candle treatment zone (67-85%) and between 10 to 66% decrease in wells impacted by the direct push candles. These results support using slow-release permanganate candles as a means of treating chlorinated solvents in low permeable aquifers. Includes Supplementary Materials

Using slow-release permanganate candles to remediate PAH-contaminated water

Surface waters impacted by urban runoff in metropolitan areas are becoming increasingly contaminated with polycyclic aromatic hydrocarbons (PAHs). Slow-release oxidant candles (paraffin–KMnO4) are a relatively new technology being used to treat contaminated groundwater and could potentially be used to treat urban runoff. Given that these candles only release permanganate when submerged, the ephemeral nature of runoff events would influence when the permanganate is released for treating PAHs. Our objective was to determine if slow-release permanganate candles could be used to degrade and mineralize PAHs. Batch experiments quantified PAH degradation rates in the presence of the oxidant candles. Results showed most of the 16 PAHs tested were degraded within 2–4 h. Using 14C-labled phenanthrene and benzo(a)pyrene, we demonstrated that the wax matrix of the candle initially adsorbs the PAH, but then releases the PAH back into solution as transformed, more water soluble products. While permanganate was unable to mineralize the PAHs (i.e., convert to CO2), we found that the permanganate-treated PAHs were much more biodegradable in soil microcosms. To test the concept of using candles to treat PAHs in multiple runoff events, we used a flow-through system where urban runoff water was pumped over a miniature candle in repetitive wet–dry, 24-h cycles. Results showed that the candle was robust in removing PAHs by repeatedly releasing permanganate and degrading the PAHs. These results provide proof-of-concept that permanganate candles could potentially provide a low-cost, low-maintenance approach to remediating PAH-contaminated water

Developing slow-release persulfate candles to treat BTEX contaminated groundwater

The development of slow-release chemical oxidants for sub-surface remediation is a relatively new technol­ogy. Our objective was to develop slow-release persulfate-paraffin candles to treat BTEX-contaminated ground­water. Laboratory-scale candles were prepared by heating and mixing Na2S2O8 with paraffin in a 2.25 to 1 ra­tio (w/w), and then pouring the heated mixture into circular molds that were 2.38 cm long and either 0.71 or 1.27 cm in diameter. Activator candles were prepared with FeSO4 or zero-valent iron (ZVI) and wax. By treat­ing benzoic acid and BTEX compounds with slow-release persulfate and ZVI candles, we observed rapid trans­formation of all contaminants. By using 14C-labeled benzoic acid and benzene, we also confirmed mineraliza­tion (conversion to CO2) upon exposure to the candles. As the candles aged and were repeatedly exposed to fresh solutions, contaminant transformation rates slowed and removal rates became more linear (zero-order); this change in transformation kinetics mimicked the observed dissolution rates of the candles. By stacking per­sulfate and ZVI candles on top of each other in a saturated sand tank (14 × 14 × 2.5 cm) and spatially sampling around the candles with time, the dissolution patterns of the candles and zone of influence were determined. Results showed that as the candles dissolved and persulfate and iron diffused out into the sand matrix, ben­zoic acid or benzene concentrations (Co = 1 mM) decreased by \u3e90% within 7 d. These results support the use of slow-release persulfate and ZVI candles as a means of treating BTEX compounds in contaminated groundwater. Includes Supplementary Materials

Modeling the release and spreading of permanganate from aerated slow-release oxidants in a laboratory flow tank

Aerated, slow-release oxidants are a relatively new technology for treating contaminated aquifers. A critical need for advancing this technology is developing a reliable method for predicting the radius of influence (ROI) around each drive point. In this work, we report a series of laboratory flow tank experiments and numerical modeling efforts designed to predict the release and spreading of permanganate from aerated oxidant candles (oxidant-wax composites). To mimic the design of the oxidant delivery system used in the field, a double screen was used in a series of flow tank experiments where the oxidant was placed inside the inner screen and air was bubbled upward in the gap between the screens. This airflow pattern creates an airlift pump that causes water and oxidant to be dispersed from the top of the outer screen and drawn in at the bottom. Using this design, we observed that permanganate spreading and ROI increased with aeration and decreased with advection. A coupled bubble flow and transport model was able to successfully reproduce observed results by mimicking the upward shape and spreading of permanganate under various aeration and advection rates

Improving the treatment of non-aqueous phase TCE in low permeability zones with permanganate

Treating dense non-aqueous phase liquids (DNAPLs) embedded in low permeability zones (LPZs) is aparticularly challenging issue for injection-based remedial treatments. Our objective was to improve thesweeping efficiency of permanganate (MnO4−) into LPZs to treat high concentrations of TCE. This wasaccomplished by conducting transport experiments that quantified the penetration of various perman-ganate flooding solutions into a LPZ that was spiked with non-aqueous phase14C-TCE. The treatments weevaluated included permanganate paired with: (i) a shear-thinning polymer (xanthan); (ii) stabilizationaids that minimized MnO2rind formation and (iii) a phase-transfer catalyst. In addition, we quantifiedthe ability of these flooding solutions to improve TCE destruction under batch conditions by develop-ing miniature LPZ cylinders that were spiked with14C-TCE. Transport experiments showed that MnO4−alone was inefficient in penetrating the LPZ and reacting with non-aqueous phase TCE, due to a distinctand large MnO2rind that inhibited the TCE from further oxidant contact. By including xanthan withMnO4−, the sweeping efficiency increased (90%) but rind formation was still evident. By including thestabilization aid, sodium hexametaphosphate (SHMP) with xanthan, permanganate penetrated 100% ofthe LPZ, no rind was observed, and the percentage of TCE oxidized increased. Batch experiments usingLPZ cylinders allowed longer contact times between the flooding solutions and the DNAPL and resultsshowed that SHMP + MnO4−improved TCE destruction by ∼16% over MnO4−alone (56.5% vs. 40.1%).These results support combining permanganate with SHMP or SHMP and xanthan as a means of treatinghigh concentrations of TCE in low permeable zones. [Includes supplementary materials

A combined chemical and biological approach to transforming and mineralizing PAHs in runoff water

The water quality of lakes, rivers and streams associated with metropolitan areas is declining from increased inputs of urban runoff that contain polycyclic aromatic hydrocarbons (PAHs). Our objective was to transform and mineralize PAHs in runoff using a combined chemical and biological approach. Using 14C-labeled phenanthrene, 14C-benzo(a)pyrene and a mixture of 16 PAHs, we found that ozone transformed all PAHs in a H2O matrix within minutes but complete mineralization to CO2 took several weeks. When urban runoff water (7.6 mg C L−1) replaced H2O as the background matrix, some delays in degradation rates were observed but transforming a mixture of PAHs was still complete within 10 min. Comparing the biodegradability of the ozonated products to the parent structures in unsaturated soil microcosms showed that the 3-ring phenanthrene was more biodegradable (as evidence by 14CO2 released) than its ozonated products but for the 5-ring benzo(a)pyrene, the products produced by ozone were much more biodegradable (22% vs. 3% mineralized). For phenanthrene, we identified diphenaldehyde as the initial degradation product produced from ozonation. By continuing to pump the ozonated products (14C-labeled diphenaldehyde or ozone-treated benzo(a)pyrene) onto glass beads coated with microorganisms, we verified that biological mineralization could be achieved in a flow-through system and mineralization rates improved with acclimation of the microbial population (i.e., time and exposure to the substrate). These results support a combined ozone and biological approach to treating PAHs in urban runoff water

Effects of Oxide Coating and Selected Cations on Nitrate Reduction by Iron Metal

Under anoxic conditions, zerovalent iron (Fe0) reduces nitrate to and magnetite (Fe3O4) is produced at near-neutral pH. removal was most rapid at low pH (2–4); however, the formation of a black oxide film at pH 5 to 8 temporarily halted or slowed reaction unless the system was augmented with Fe2+, Cu2+, or Al3+. Bathing the corroding Fe0 in a Fe2+ solution greatly enhanced nitrate reduction at near-neutral pH and coincided with the formation of a black precipitate. X-ray diffractometry and scanning electron microscopy confirmed that both the black precipitate and black oxide coating on the iron surface were magnetite. In this system, ferrous iron was determined to be a partial contributor to nitrate removal, nitrate reduction was not observed in the absence of Fe0. Nitrate removal was also enhanced by augmenting the Fe0–H2O system with Fe3+, Cu2+, or Al3+ but not Ca2+, Mg2+, or Zn2+. Our research indicates that a magnetite coating is not a hindrance to nitrate reduction by Fe0, provided sufficient aqueous Fe2+ is present in the system