A review of the application of cerium and lanthanum in phosphorus removal during wastewater treatment: Characteristics, mechanism, and recovery.

Owing to their strong bond with anions, rare earth elements (REEs) are prime contenders in wastewater treatment to meet the stringent phosphorus (P) effluent quality requirements. REEs outcompete traditional metals to abate phosphorus. The application of lanthanides in wastewater treatment is mainly through adsorption, where REEs are incorporated into a carrier matrix to improve the adsorption capacity. As coagulants, information on the performance of lanthanides is lacking. In this review, the performance of major water coagulants (iron and aluminum) is discussed and compared to two lanthanides: cerium and lanthanum. The use of lanthanides as adsorbents and as coagulants is elucidated during P treatment. The recovery of P and REEs is also discussed. Where details were lacking in the literature, experiments were conducted to fill these research gaps. Using REEs as adsorbents limits their P precipitation potential; as coagulants, REE capacity is 520.79 mg P/g La3+ and 469.96 mg P/g Ce3+. In addition, as coagulants, they are not affected by pH (3.0 < pH < 10.0); however, carbonates and sulfate are the major species that can reduce the performance of REEs during P treatment. REE-P precipitation is orchestrated through the formation of an REE-PO4 bond. Unfortunately, this strong bond between lanthanides and phosphate makes phosphate recovery almost impractical. If the goal is to recover REEs and reuse P in other applications like fertilizers, REEs are not the best candidates. We recommend additional research dedicated to understanding lanthanide coagulants in typical wastewater treatment facilities and their release from phosphate precipitates under different environmental conditions.

Evaluation of disinfection byproducts for their ability to affect mitochondrial function.

In the race to deliver clean water to communities through potable water reuse, disinfection and water quality assessment are and will continue to be fundamental factors. There are over 700 disinfection byproducts (DBPs) in water; evaluating each compound is practically impossible and very time consuming. A bioanalytical approach could be an answer to this challenge. In this work, the response of four major classes of DBPs toward mitochondrial membrane potential (ΔΨm) and cytoplasmic adenosine triphosphate (C-ATP) was investigated with human carcinoma (HepG2) cells. Within 90 min of cell exposure, only the haloacetic acid (HAA) mixture caused a cytotoxic response as measured by C-ATP. All four groups (haloacetonitriles (HANs), trihalomethanes (THMs), nitrosamines (NOAs), and HAAs) responded well to ΔΨm, R2 > 0.70. Based on the half-maximum concentration that evoked a 50% response in ΔΨm, the response gradient was HANs >> HAAs ∼ THM > NOAs. The inhibition of the ΔΨm by HANs is driven by dibromoacetonitrile (DBAN), while dichloroacetonitrile (DCAN) did not cause a significant change in the ΔΨm at less than 2000 µM. A mixture of HANs exhibited an antagonistic behavior on the ΔΨm compared to individual compounds. If water samples are concentrated to increase HAN concentrations, especially DBAN, then ΔΨm could be used as a biomonitoring tool for DBP toxicity.

Toxicity of lanthanide coagulants assessed using four in vitro bioassays.

Rare earth element (REE) coagulants are prime contenders in wastewater treatment plants to remove phosphorus; unlike typical coagulants, they are not affected by pH. However, the use of REEs in wastewater treatment could mean increased human exposure to lanthanides (Ln) through wastewater effluent discharge to the environment or through water reuse. Information on the toxicity of lanthanides is scarce and, where available, there are conflicting views. Using in vitro bioassays, we assessed lanthanide toxicity by evaluating four relevant endpoints: the change in mitochondrial membrane potential (Δψm), intracellular adenosine triphosphate (I-ATP), genotoxicity, and cell viability. At less than 5000 µmol-Ln3+/L, lanthanides increased the Δψm, while above 5000 µmol-Ln3+/L, the Δψm level plummeted. The measure of I-ATP indicated constant levels of ATP up to 250 µmol-Ln3+/L, above which the I-ATP decreased steadily; the concentration of La, Ce, Gd, and Lu that triggered half of the cells to become ATP-inactive is 794, 1505, 1488, 1115 µmol-Ln3+/L, respectively. Although La and Lu accelerated cell death in shorter studies (24 h), chronic studies using three cell growth cycles showed cell recovery. Lanthanides exhibited antagonistic toxicity at less than 1000 µmol-Ln3+/L. However, the introduction of heavy REEs in a solution amplified lanthanide toxicity. Tested lanthanides appear to pose little risk, which could pave the way for lanthanide application in wastewater treatment.

A novel assay to measure tertiary and quaternary amines in wastewater: An indicator for NDMA wastewater precursors.

This study examined the potential of using a novel bulk amine assay as an approximation for the tertiary and quaternary amine load in wastewaters and surface water samples, and this approximation was compared to N-nitrosodimethylamine (NDMA) formation potential using chloramines. An existing colorimetric method was examined and optimized for the detection of amines in environmental water samples. The method consists of liquid-liquid extraction followed by a catalyzed reaction to form a yet-undefined product that is known to be both a strong chromophore and fluorophore. Previous work verified that this reaction was effectively catalyzed by a number of compounds containing tertiary and quaternary amine moieties. Many tertiary and quaternary compounds are also efficient producers of NDMA under chloramination conditions, and a linear correlation was consequently derived from the bulk amine signals vs. NDMA formation potential in various wastewater samples (R2 = 0.74; n = 24; p-value < 0.05). The results provide evidence that approximately 2% of the tertiary and quaternary amines measured can form NDMA and an estimated 0.01-1.3% of nitrogen in dissolved organic nitrogen originates from these bulk amines. The normalization of NDMA concentration by the amine measurement revealed that ozone effectively destroyed those tertiary and quaternary amine structures more likely to form NDMA in treated wastewater samples. This bulk amine assay illustrates that proxy measurements of tertiary and quaternary amines can be linked to the NDMA formation potential of a given sample, and this approach may prove useful as a characterizing tool for NDMA precursors in wastewater.

Relative Importance of Different Water Categories as Sources of N-Nitrosamine Precursors.

A comparison of loadings of N-nitrosamines and their precursors from different source water categories is needed to design effective source water blending strategies. Previous research using Formation Potential (FP) chloramination protocols (high dose and prolonged contact times) raised concerns about precursor loadings from various source water categories, but differences in the protocols employed rendered comparisons difficult. In this study, we applied Uniform Formation Condition (UFC) chloramination and ozonation protocols mimicking typical disinfection practice to compare loadings of ambient specific and total N-nitrosamines as well as chloramine-reactive and ozone-reactive precursors in 47 samples, including 6 pristine headwaters, 16 eutrophic waters, 4 agricultural runoff samples, 9 stormwater runoff samples, and 12 municipal wastewater effluents. N-Nitrosodimethylamine (NDMA) formation from UFC and FP chloramination protocols did not correlate, with NDMA FP often being significant in samples where no NDMA formed under UFC conditions. N-Nitrosamines and their precursors were negligible in pristine headwaters. Conventional, and to a lesser degree, nutrient removal wastewater effluents were the dominant source of NDMA and its chloramine- and ozone-reactive precursors. While wastewater effluents were dominant sources of TONO and their precursors, algal blooms, and to a lesser degree agricultural or stormwater runoff, could be important where they affect a major fraction of the water supply.

N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds.

Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging.

Impact of secondary treatment types and sludge handling processes on estrogen concentration in wastewater sludge.

Endocrine-disrupting compounds (EDCs), such as estrogen, are known to be present in the aquatic environment at concentrations that negatively affect fish and other wildlife. Wastewater treatment plants (WWTPs) are major contributors of EDCs into the environment. EDCs are released via effluent discharge and land application of biosolids. Estrogen removal in WWTPs has been studied in the aqueous phase; however, few researchers have determined estrogen concentration in sludge. This study focuses on estrogen concentration in wastewater sludge as a result of secondary treatment types and sludge handling processes. Grab samples were collected before and after multiple treatment steps at two WWTPs receiving wastewater from the same city. The samples were centrifuged into aqueous and solid phases and then processed using solid phase extraction. Combined natural estrogens (estrone, estradiol and estriol) were measured using an enzyme-linked immunosorbent assay (ELISA) purchased from a manufacturer. Results confirmed that activated sludge treatments demonstrate greater estrogen removal compared to trickling filters and mass concentration of estrogen was measured for the first time on trickling filter solids. Physical and mechanical sludge treatment processes, such as gravity thickeners and centrifuges, did not significantly affect estrogen removal based on mass balance calculations. Dissolved air flotation thickening demonstrated a slight decrease in estrogen concentration, while anaerobic digestion resulted in increased mass concentration of estrogen on the sludge and a high estrogen concentration in the supernatant. Although there are no state or federally mandated discharge effluent standards or sludge application standards for estrogen, implications from this study are that trickling filters would need to be exchanged for activated sludge treatment or followed by an aeration basin in order to improve estrogen removal. Also, anaerobic digestion may need to be replaced with aerobic digestion for sludge that is intended for land application.