Expanding Perspectives of Element Cycling from 1970 to 2020: The Influence of Stumm and Morgan.

There has been significant advancement in understanding of element cycles over the past 50 years, and the contributions of the three editions of Aquatic Chemistry by Stumm and Morgan on the critical role of reactions in the aqueous phase on the global cycles of elements have been substantial. The primary focus of investigation of biogeochemical element cycles has been on the "grand nutrients" carbon, nitrogen, phosphorus, and sulfur. The basic chemistry and chemical systems perspective of Aquatic Chemistry helped elucidate the cycles of these elements. Most of the element cycling research beyond the grand nutrients has occurred in the past 20 years and has focused on commodity metals in widespread use, that is, the "technological nutrients". Focus in Aquatic Chemistry on metal chemistry has contributed to understanding of metal cycles. Development of integrated anthropogenic-biogeochemical cycles of metals, led by Graedel and collaborators, has revealed that anthropogenic mobilization of metals dominates the cycles. Integrated "anthrobiogeochemical" element cycles provide for more detailed understanding of sources and their cascading impacts, and enable identification of priorities for source control and/or element recovery. The fundamentals of water chemistry and their application in engineered and natural systems, as presented so effectively in Aquatic Chemistry, have contributed to advancement of anthrobiogeochemical cycle development and analysis and, directly or indirectly, to the scholars who will continue to evolve the understanding and use of element cycles in the years ahead.

Pioneering groundwater contamination investigation, research, and in situ treatment.

The 1972 paper by Professor Jack McKee of the California Institute of Technology, consulting engineer Finley Laverty and Raymond Hertzel of the California Regional Water Quality Control Board-Los Angeles (McKee et al., 1972) was an early, important contribution to the understanding of groundwater contamination with organic liquids and to the integrated use of field, laboratory, and modeling studies to develop remediation approaches. The work presented in the paper was ahead of the curve and helped provide the foundation for the intense research, development, and education in investigation and remediation of groundwater contamination problems that began around 1980 and lasted for two decades. Reading the paper in the current context of more than 40 years of research and field experience provides perspective on how little was known in 1972 about groundwater contamination and how to address it, and how well-formulated and forward-looking was the work of McKee et al. PRACTITIONER POINTS: McKee et al. (1972) was an early, important contribution to the understanding of groundwater contamination with organic liquids and to the integrated use of field, laboratory and modeling studies to develop remediation approaches. McKee et al. present the results of site investigation and remediation planning studies for a large-scale groundwater contamination site in the Los Angeles-Glendale, California area. Four specific remediation goals were established, and a comprehensive program of site investigation, research, and modeling was developed to support the achievement of the remediation goals. The comprehensive site investigation and remedial planning involving field, laboratory, and modeling studies described by McKee et al. was a forerunner of what came into standard contaminated site remediation practice in the 1980s and 1990s.

Water Supply Risk in the United States 2015-2050 Considering Projected Changes in Population and Thermoelectric Power Demand.

Examination of water supply risk is important to identify areas of potential insecurity and prioritize allocation of resources. This work builds on and advances a previous U.S. water supply risk analysis developed at county-scale resolution, which did not account for water flow between counties and identified some counties on major rivers as being at high risk. This limitation is addressed in the present study. The analysis utilized data from U.S. Geological Survey water use reports to assess current water supply risk and also projected water supply risk in 2050. Flow volumes were calculated using the Water Supply Sustainability Index (WaSSI) tool developed by the USDA Forest Service, enabling the analysis to account for changes in climate and hydrology and changes in water demand. A modified Water Risk Index (WRI) was formulated, including five factors to which scaled values were assigned. Results indicate that accounting for natural transfers of water in counties in addition to local precipitation reduced the risk profile of many counties, with a maximum of 36 classified as high or very high risk, compared to over 400 identified in the highest risk category in the previous analysis.

Adsorption kinetics, thermodynamics, and isotherm studies for functionalized lanthanide-chelating resins.

Conventional ion exchange resins are widely utilized to remove metals from aqueous solutions, but their limited selectivity precludes dilute ion extraction. This research investigated the adsorption performance of ligand-functionalized resins towards rare earth elements (REE). Functionalized resin particles were synthesized by grafting different ligands (diethylenetriaminepentaacetic dianhydride (DTPADA), phosphonoacetic acid (PAA), or N,N-bis(phosphonomethyl)glycine (BPG)) onto pre-aminated polymeric adsorbents (diameter ∼ 0.6 mm). Lanthanide uptake trends were evaluated for the functionalized resins using batch adsorption experiments with a mixture of three REEs (Nd, Gd, and Ho at 0.1-1000 mg/L each). Resin physical-chemical properties were determined by measuring their surface area, ligand concentrations, and acidity constants. The aminated supports contained 4.0 mmol/g primary amines, and ligand densities for the functionalized resins were 0.33 mmol/g (PAA), 0.22 mmol/g (BPG), and 0.42 mmol/g (DTPADA). Kinetic studies revealed that the functionalized resins followed pseudo-second order binding kinetics with rates limited by intraparticle diffusion. Capacity estimates for total REE adsorption based on Langmuir qMax were 0.12 mg/g (amine; ≈ 0.77 µmol/g), 5.0 mg/g (PAA; ≈ 32.16 µmol/g), 3.0 mg/g (BPG; ≈ 19.30 µmol/g), and 2.9 mg/g (DTPADA; ≈ 18.65 µmol/g). Attaching ligands to the aminated resins greatly improved their REE binding strength and adsorption efficiency.

Determination of Rare Earth Elements in Hypersaline Solutions Using Low-Volume, Liquid-Liquid Extraction.

Complex, hypersaline brines-including those coproduced with oil and gas, rejected from desalination technologies, or used as working fluids for geothermal electricity generation-could contain critical materials such as the rare earth elements (REE) in valuable concentrations. Accurate quantitation of these analytes in complex, aqueous matrices is necessary for evaluation and implementation of systems aimed at recovering those critical materials. However, most analytical methods for measuring trace metals have not been validated for highly saline and/or chemically complex brines. Here we modified and optimized previously published liquid-liquid extraction (LLE) techniques using bis(2-ethylhexyl) phosphate as the extractant in a heptane diluent, and studied its efficacy for REE recovery as a function of three primary variables: background salinity (as NaCl), concentration of a competing species (here Fe), and concentration of dissolved organic carbon (DOC). Results showed that the modified LLE was robust to a range of salinity, Fe, and DOC concentrations studied as well as constant, elevated Ba concentrations. With proper characterization of the natural samples of interest, this method could be deployed for accurate analysis of REE in small volumes of hyper-saline and chemically complex brines.

A method for preparation and cleaning of uniformly sized arsenopyrite particles.

BACKGROUND: The oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 150-250 µm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from the surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM-EDS). RESULTS: Results indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface. CONCLUSIONS: Although sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.

Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques.

Rare earth element distributions and trends in natural waters with a focus on groundwater.

Systematically varying properties and reactivities have led to focused research of the environmental forensic capabilities of rare earth elements (REE). Increasing anthropogenic inputs to natural systems may permanently alter the natural signatures of REE, motivating characterization of natural REE variability. We compiled and analyzed reported dissolved REE concentration data over a wide range of natural water types (ground-, ocean, river, and lake water) and groundwater chemistries (e.g., fresh, brine, and acidic) with the goal of quantifying the extent of natural REE variability, especially for groundwater systems. Quantitative challenges presented by censored data were addressed with nonparametric distributions and regressions. Reported measurements of REE in natural waters range over nearly 10 orders of magnitude, though the majority of measurements are within 2-4 orders of magnitude, and are highly correlated with one another. Few global correlations exist among dissolved abundance and bulk solution properties in groundwater, indicating the complex nature of source-sink terms and the need for care when comparing results between studies. This collection, homogenization, and analysis of a disparate literature facilitates interstudy comparison and provides insight into the wide range of variables that influence REE geochemistry.

Factors governing change in water withdrawals for U.S. industrial sectors from 1997 to 2002.

The United States Geological Survey (USGS) reports that U.S. water withdrawals have been steady since 1980, but the population and economy have grown since then. This implies that other factors have contributed to offsetting decreases in water withdrawals. Using water withdrawal data from USGS and economic data from Bureau of Economic Analysis (BEA), direct and total water withdrawals were estimated for 134 industrial summary sectors in the 1997 U.S. economic input-output (EIO) table and 136 industrial sectors in the 2002 EIO table. Using structural decomposition analysis (SDA), the change in water withdrawals for the economy from 1997 to 2002 was allocated to changes in population, GDP per capita, water use intensity, production structure, and consumption patterns. The changes in population, GDP per capita, and water use intensity led to increased water withdrawals, while the changes in production structure and consumption patterns decreased water withdrawals from 1997 to 2002. Consumption patterns change was the largest net contributor to the change in water withdrawals. The model was used to predict aggregate changes in total water withdrawals from 2002 to 2010 due to known changes in population and GDP per capita; a more complete model assessment must await release of updated data on USGS water withdrawals and EIO data.

Comprehensive Evaluation of Biological Growth Control by Chlorine-Based Biocides in Power Plant Cooling Systems Using Tertiary Effluent.

Recent studies have shown that treated municipal wastewater can be a reliable cooling water alternative to fresh water. However, elevated nutrient concentration and microbial population in wastewater lead to aggressive biological proliferation in the cooling system. Three chlorine-based biocides were evaluated for the control of biological growth in cooling systems using tertiary treated wastewater as makeup, based on their biocidal efficiency and cost-effectiveness. Optimal chemical regimens for achieving successful biological growth control were elucidated based on batch-, bench-, and pilot-scale experiments. Biocide usage and biological activity in planktonic and sessile phases were carefully monitored to understand biological growth potential and biocidal efficiency of the three disinfectants in this particular environment. Water parameters, such as temperature, cycles of concentration, and ammonia concentration in recirculating water, critically affected the biocide performance in recirculating cooling systems. Bench-scale recirculating tests were shown to adequately predict the biocide residual required for a pilot-scale cooling system. Optimal residuals needed for proper biological growth control were 1, 2-3, and 0.5-1 mg/L as Cl2 for NaOCl, preformed NH2Cl, and ClO2, respectively. Pilot-scale tests also revealed that Legionella pneumophila was absent from these cooling systems when using the disinfectants evaluated in this study. Cost analysis showed that NaOCl is the most cost-effective for controlling biological growth in power plant recirculating cooling systems using tertiary-treated wastewater as makeup.

Control of biological growth in recirculating cooling systems using treated secondary effluent as makeup water with monochloramine.

Secondary-treated municipal wastewater, an abundant and widely distributed impaired water source, is a promising alternative water source for thermoelectric power plant cooling. However, excessive biological growth is a major challenge associated with wastewater reuse in cooling systems as it can interfere with normal system operation as well as enhance corrosion and scaling problems. Furthermore, possible emission of biological aerosols (e.g., Legionella pneumophila) with the cooling tower drift can lead to public health concerns within the zone of aerosol deposition. In this study, the effectiveness of pre-formed and in-situ-formed monochloramine was evaluated for its ability to control biological growth in recirculating cooling systems using secondary-treated municipal wastewater as the only makeup water source. Bench-scale studies were compared with pilot-scale studies for their ability to predict system behavior under realistic process conditions. Effectiveness of the continuous addition of pre-formed monochloramine and monochloramine formed in-situ through the reaction of free chlorine with ammonia in the incoming water was evaluated in terms of biocide residual and its ability to control both planktonic and sessile microbial populations. Results revealed that monochloramine can effectively control biofouling in cooling systems employing secondary-treated municipal wastewater and has advantages relative to use of free chlorine, but that bench-scale studies seriously underestimate biocide dose and residual requirements for proper control of biological growth in full-scale systems. Pre-formed monochloramine offered longer residence time and more reliable performance than in-situ-formed monochloramine due to highly variable ammonia concentration in the recirculating water caused by ammonia stripping in the cooling tower. Pilot-scale tests revealed that much lower dosing rate was required to maintain similar total chlorine residual when pre-formed monochloramine was used as compared to in-situ-formed monochloramine. Adjustment of biocide dose to maintain monochloramine residual above 3mg/L is needed to achieve successful biological growth control in recirculating cooling systems using secondary-treated municipal effluent as the only source of makeup water.

Mineral scaling mitigation in cooling systems using tertiary-treated municipal wastewater.

Treated municipal wastewater (MWW) is recognized as a significant potential source of cooling water for power generation. One of the key challenges for the successful use of the effluent from wastewater treatment facilities for cooling is the potential for significant mineral scaling when the raw water is concentrated as much as 4-6 times in recirculating cooling systems. Previous bench- and pilot-scale tests have shown that commonly used phosphorus- and polymer- based scaling inhibitors are ineffective when secondary-treated municipal wastewater (MWW) is used as make-up. In this study, two types of tertiary-treated municipal wastewaters, namely secondary-treated MWW with pH adjustment (MWW_pH) and secondary-treated MWW subjected to nitrification and sand filtration (MWW_NF) were evaluated as the sole source of make-up water for recirculating cooling systems. Both laboratory studies and pilot-scale tests revealed that adjusting the pH to 7.8 could reduce the mineral scaling rate by more than 80% without causing any significant corrosion problems. In contrast to MWW, where calcium carbonate was the dominant scaling mineral, the main component of mineral scale in MWW_pH was calcium phosphate. Both static and dynamic bench-scale tests indicated that scaling would not be a significant concern when MWW_NF is used as the make-up water in recirculating cooling systems operated at 4-6 cycles of concentration (CoC). Extended pilot-scale studies confirmed that MWW_NF is suitable makeup water for power plant cooling systems and that no anti-scaling chemicals would be required.

Corrosion control when using passively treated abandoned mine drainage as alternative makeup water for cooling systems.

Passively treated abandoned mine drainage (AMD) is a promising alternative to fresh water as power plant cooling water system makeup water in mining regions where such water is abundant. Passive treatment and reuse of AMD can avoid the contamination of surface water caused by discharge of abandoned mine water, which typically is acidic and contains high concentrations of metals, especially iron. The purpose of this study was to evaluate the feasibility of reusing passively treated AMD in cooling systems with respect to corrosion control through laboratory experiments and pilot-scale field testing. The results showed that, with the addition of the inhibitor mixture orthophosphate and tolyltriazole, mild steel and copper corrosion rates were reduced to acceptable levels (< 0.127 mm/y and < 0.0076 mm/y, respectively). Aluminum had pitting corrosion problems in every condition tested, while cupronickel showed that, even in the absence of any inhibitor and in the presence of the biocide monochloramine, its corrosion rate was still very low (0.018 mm/y).

Escalating water demand for energy production and the potential for use of treated municipal wastewater.

To ensure sufficient thermoelectric power production in the future, the use of alternative water sources to replace freshwater consumption in power plants will be required. The amount of municipal wastewater (MWW) being produced and its widespread availability merit the investigation of this potential source of cooling water. This is particularly important for thermoelectric power plants in regions where freshwater is not readily available. Critical regulatory and technical challenges for using MWW as makeup water in recirculating cooling systems are examined. The existing regulations do not prohibit wastewater reuse for power plant cooling. The challenges of controlling corrosion, mineral scaling, and biofouling in recirculating cooling systems need to be carefully considered and balanced in a holistic fashion. Initial investigations suggest that many of these challenges can be surmounted to ensure the use of MWW in recirculating cooling systems.

Control of mineral scale deposition in cooling systems using secondary-treated municipal wastewater.

Secondary-treated municipal wastewater (MWW) is a promising alternative to freshwater as power plant cooling system makeup water, especially in arid regions. A prominent challenge for the successful use of MWW for cooling is potentially severe mineral deposition (scaling) on pipe surfaces. In this study, theoretical, laboratory, and field work was conducted to evaluate the mineral deposition potential of MWW and its deposition control strategies under conditions relevant to power plant cooling systems. Polymaleic acid (PMA) was found to effectively reduce scale formation when the makeup water was concentrated four times in a recirculating cooling system. It was the most effective deposition inhibitor of those studied when applied at 10 mg/L dosing level in a synthetic MWW. However, the deposition inhibition by PMA was compromised by free chlorine added for biogrowth control. Ammonia present in the wastewater suppressed the reaction of the free chlorine with PMA through the formation of chloramines. Monochloramine, an alternative to free chlorine, was found to be less reactive with PMA than free chlorine. In pilot tests, scaling control was more challenging due to the occurrence of biofouling even with effective control of suspended bacteria. Phosphorous-based corrosion inhibitors are not appropriate due to their significant loss through precipitation reactions with calcium. Chemical equilibrium modeling helped with interpretation of mineral precipitation behavior but must be used with caution for recirculating cooling systems, especially with use of MWW, where kinetic limitations and complex water chemistries often prevail.

Corrosion control when using secondary treated municipal wastewater as alternative makeup water for cooling tower systems.

Secondary treated municipal wastewater is a promising alternative to fresh water as power plant cooling water system makeup water, especially in arid regions. Laboratory and field testing was conducted in this study to evaluate the corrosiveness of secondary treated municipal wastewater for various metals and metal alloys in cooling systems. Different corrosion control strategies were evaluated based on varied chemical treatment. Orthophosphate, which is abundant in secondary treated municipal wastewater, contributed to more than 80% precipitative removal of phosphorous-based corrosion inhibitors. Tolyltriazole worked effectively to reduce corrosion of copper (greater than 95% inhibition effectiveness). The corrosion rate of mild steel in the presence of free chlorine 1 mg/L (as Cl2) was approximately 50% higher than in the presence of monochloramine 1 mg/L (as Cl2), indicating that monochloramine is a less corrosive biocide than free chlorine. The scaling layers observed on the metal alloys contributed to corrosion inhibition, which could be seen by comparing the mild steel 21-day average corrosion rate with the last 5-day average corrosion rate, the latter being approximately 50% lower than the former.