Management of per- and polyfluoroalkyl substances (PFAS)-laden wastewater sludge in Maine: Perspectives on a wicked problem.

This article discusses the challenges and potential solutions for managing wastewater sludge that contains per- and polyfluoroalkyl substances (PFAS), using the experience in Maine as a guide toward addressing the issue nationally. Traditional wastewater treatment, designed to remove excess organic waste and nutrients, does not eliminate persistent toxic pollutants like PFAS, instead partitioning the chemicals between discharged effluent and the remaining solids in sludge. PFAS chemistry, the molecular size, the alkyl chain length, fluorine saturation, the charge of the head group, and the composition of the surrounding matrix influence PFAS partitioning between soil and water. Land application of sludge, incineration, and storage in a landfill are the traditional management options. Land application of Class B sludge on agricultural fields in Maine peaked in the 1990s, totaling over 2 × 106 cu yd over a 40-year period and has contaminated certain food crops and animal forage, posing a threat to the food supply and the environment. Additional Class A EQ (Exceptional Quality) composted sludge was also applied to Maine farmland. The State of Maine banned the land application of wastewater sludge in August 2022. Most sludge was sent to the state-owned Juniper Ridge Landfill, which accepted 94 270 tons of dewatered sludge in 2022, a 14% increase over 2019. Between 2019 and 2022, the sum of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) concentrations in sludge sent to the landfill ranged from 1.2 to 104.9 ng/g dw. In 2022, the landfill generated 71.6 × 106 l of leachate. The concentration of sum of six PFAS in the leachate increased sixfold between 2021 and 2022, reaching 2 441 ng/l. The retention of PFAS within solid-waste landfills and the potential for long-term release of PFAS through liners into groundwater require ongoing monitoring. Thermal treatment, incineration, or pyrolysis can theoretically mineralize PFAS at high temperatures, yet the strong C-F bond and reactivity of fluorine require extreme temperatures for complete mineralization. Future alternatives may include interim options such as preconditioning PFAS with nonpolar solvents prior to immobilization in landfills, removing PFAS from leachate, and interrupting the cycle of PFAS moving from landfill, via leachate, to wastewater treatment, and then back to the landfill via sludge. Long-term solutions may involve destructive technologies such as electron beam irradiation, electrochemical advanced oxidation, or hydrothermal liquefaction. The article highlights the need for innovative and sustainable solutions for managing PFAS-contaminated wastewater sludge.

Kinetics and equilibrium properties of the biosorption of Cu2+ by algae.

The purpose of this study was to examine the kinetics and equilibrium properties of freshwater algae with Cu(2+). This was a model system to explore using algae as biosensors for water quality. Methods included making luminescence measurements (fluorescence) and copper ion-selective electrode (CuISE) measurements vs. time to obtain kinetic data. Results were analyzed using a pseudo-first-order model to calculate the rate constants of Cu(2+) uptake by algae: k (p(Cu-algae)) = 0.0025 ± 0.0006 s(-1) by CuISE and k (p(Cu-algae)) = 0.0034 ± 0.0011 s(-1) by luminescence. The binding constant of Cu-algae, K (Cu-algae), was 1.62 ± 0.07 × 10(7) M(-1). Fluorescence results analyzed using the Stern-Volmer relationship indicate that algae have two types of binding sites of which only one appears to affect quenching. The fluorescence-based method was found to be able to detect the reaction of algae with Cu(2+) quickly and at a detection limit of 0.1 mg L(-1).

Release of nitrogen and trace metal species from field stacked biosolids.

Concerns over elevated nitrate (NO3-) levels found in groundwater near former biosolid stockpiling locations resulted in the Maine Department of Environmental Protection (MDEP) imposing stricter regulations governing the stockpiling of biosolids in October 2002. The goals of this study were to measure the amount and speciation of nitrogen (N) and trace metals leaving stockpiled biosolids and travelling through the soil column. The biosolids were placed on plastic-lined cells to collect all leachate. Ammonium (NH4+), ranging from 2000 to 4900 mg L(-1), was the dominant N species (90% of total N) in the leachate from the Class B lime-stabilized biosolids in the lined cell experiment. Nitrate (NO3-) and nitrite (NO2-) concentrations were negligible, remaining below 0.25 and 0.1 mg L(-1), respectively. Dissolved organic carbon (DOC) concentrations as high as 8900 mg L(-1) and chemical oxygen demand (COD) as high as 37 000 mg L(-1) were measured in the leachate leaving the lined cell. Fifteen zero-tension pan lysimeters (ZTP-lysimeter) were installed in a 90 m2 plot at depth intervals of 30, 60, and 100 cm. Leachate passing through the soil column underlying the biosolids stockpile was collected in the ZTP-lysimeters. The average ZTP-lysimeter NH4+ concentrations ranged from 1400 mg L(-1) at 60 cm depth to 145 mg L(-1) at 90 cm depth. The average ZTP-lysimeter DOC concentrations ranged from 2000 mg L(-1) at 60 cm to 525 mg L(-1) at 90 cm. Trace metal determinations of the leachate collected from the lined cell and ZTP-lysimeters showed arsenic loading rates exceeded the state limits of 0.5 kg ha(-1) year(-1) by an order of magnitude. Arsenic concentrations were in excess of several thousand milligrams per litre in the lined-cell leachate and several hundred milligrams per litre in the ZTP-lysimeters as deep as 90 cm under the biosolid stockpile. Phosphorus, iron and manganese in excess of several thousand milligrams per litre were observed in both the lined-cell leachate and ZTP-lysimeters. Significant concentrations of other trace metals were found at depth in the zero-tension ZTP-lysimeter plot. Trace metals were largely mobilized by the DOC from the biosolids and due to the presence of anaerobic environment, especially in the underlying soil.

Emerging technologies for identification of disinfection byproducts: GC/FT-ICR MS characterization of solvent artifacts.

Water samples from a local water treatment plant were analyzed, using gas chromatography Fourier transform ion cyclotron resonance mass spectrometry (GC/FT-ICR MS), to identify potential disinfection byproducts (DBPs). Both liquid-liquid extraction (LLE) and solid-phase microextraction (SPME) techniques were used for sample preparation prior to GC/MS analyses. Based on the averaged mass measurement accuracy (MMA) of better than five parts-per-million (<5 ppm), multiple solvent artifacts were identified. It is shown that solventless SPME can be utilized to reduce potential interferences from solvent stabilizers. Six DBPs were detected and their molecular compositions were assigned at a high level of confidence. At the ppb concentration ranges and in the broadband mass spectral detection mode, internally calibrated mass spectra provided concurrent high resolution (resolving power M/deltaM50% > 30,000 at m/z values -110) and MMA of better than one part-per-million (MMA < 1 ppm). The use of thermochemical data, such as proton affinities, as a complementary tool to enhance analytical resolution is also demonstrated.

Background mercury concentrations in river water in Maine, U.S.A.

Mercury concentrations in 58 rivers in Maine was measured to range from below detection up to 7.01 ng L(-1) and averaged 1.80 +/- 1.29 ng L(-1). The concentration gradient for mercury in rivers across the state was not uniform. Mercury strongly correlated with dissolved organic carbon (DOC) and aluminum, and less strongly with copper, lead, and zinc. Mercury exhibited significant differences in correlations with chemical variables and local geology when partitioned by flow state (high or low). Mercury concentrations were greatest in rivers flowing across either wacke-type bedrock at low metamorphic grade, or glacial-till deposits. Elevated concentrations of mercury formed a locus in northern Maine under both high and low-flow states while in southwestern Maine a locus formed only during high-flow states. These regional differences were statistically significant when compared by geographical location. We suggest that there is a bedrock source of mercury in northeastern Maine that is diluted during periods of high runoff. The elevated concentrations detected under high-flow states, as noted in southwestern Maine, may reflect mercury released from storage in association with DOC during periods of high runoff. The association of mercury with flow state indicates that watershed processes and local geology can modulate the concentration of mercury in rivers.