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.

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.

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.

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.

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.

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.

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.

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).

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.

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.

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.

A method for generating uniform size-segregated pyrite particle fractions.

BACKGROUND: Standardized sample preparation techniques allow comparison of pyrite dissolution experiments under diverse conditions. Our objective was to assess dry and wet sieving preparation methodologies, and to develop a reproducible technique that yields uniformly size-distributed material within a limited size range of interest. RESULTS: Here, we describe a wet sieving preparation method that successfully concentrates pyrite particles within a 44-75 microm diameter range. In addition, this technique does not require a post-processing cleanup step to remove adhering particles, as those particles are removed during the procedure. We show that sample preparation methods not only affect the pyrite size distribution, but also apparent dissolution rates. CONCLUSION: The presented methodology is non-destructive to the sample, uses readily available chemical equipment within the laboratory, and could be applied to minerals other than pyrite.

Long-term changes in quality of discharge water from abandoned underground coal mines in Uniontown Syncline, Fayette County, PA, USA.

Changes in water quality over 25 years have been documented for discharges from an extensive network of abandoned underground coal mines in the Uniontown Syncline, Fayette County, PA, USA. A baseline study of 136 mine discharges in the syncline was conducted in 1974-1975. In 1998-2000, follow-up water flow and quality monitoring was conducted at 21 selected discharges for 2 years to assess the degree of mine water-quality improvement since 1974-1975. The data from the two periods of time were compared, with consideration of differences in measurement methods. The degree and rate of water-quality improvement was found to be highly dependent on the amount and duration of flooding in the mine voids. Water quality of discharges from the substantially flooded mine voids improved significantly, going from acidic water with high sulfate and iron concentrations in 1974-1975 to alkaline water with substantially lower sulfate and iron concentrations in 1998-2000. In contrast, the water quality in the unflooded mines showed less improvement over the 25 years between studies. The water discharging from the unflooded mines in 1974-1975 was acidic with high sulfate concentrations and in 1998-2000 was still acidic but showed somewhat lower sulfate and iron concentrations, reflecting depletion of readily available pyrite. The data obtained provide insight into the potential and rate of natural amelioration of mine water quality in different abandoned underground coal mine systems.

Ferrocyanide adsorption on aluminum oxides.

Ferrocyanide (Fe(CN)6(4-)) adsorption onto gamma-alumina ( gamma-Al2O3(s) ) and gibbsite (Al(OH)3(s)) was investigated over a wide pH range and at various solid loadings. Batch experiments were performed using 100-ml solutions (I = 0.01 M NaCl) dosed with 1.0 mgl(-1) Fe(CN)6(4-) as CN. Equilibrium adsorption-pH edges were developed for 0.3, 0.6, 1.2, and 2.0 gl(-1) gamma-Al(2)O3(s) and 25 gl(-1) Al(OH)3(s). Ferrocyanide adsorption increased as pH decreased, consistent with the general pH dependence for adsorption of anions onto oxide minerals. Ferrocyanide adsorption onto Al(OH)3(s) was approximately 300 times lower than onto gamma-Al(2)O3(s) on a unit weight basis due to the higher surface reactivity of the gamma-Al(2)O3(s). Ferrocyanide adsorption onto gamma-Al(2)O3(s) was significantly greater than has been reported for goethite (FeOOH(s)), and both gamma-Al(2)O3(s) and FeOOH(s) adsorbed ferrocyanide to a greater extent than Al(OH)3(s) . The investigation showed that ferrocyanide can adsorb significantly onto aluminum oxides spanning a range of crystallinity and properties, with the extent of adsorption highly dependent on pH, the solid crystalline structure, and associated surface reactivity.

Effects of nitrosation on the formation of cyanide in publicly owned treatment works secondary effluent.

Cyanide has been detected in the effluents of some publicly owned treatment works (POTWs) at levels exceeding the influent concentration. The presence of nitrite ion (NO2-) as a common constituent in domestic wastewater effluents may play an important role in the formation of cyanide through reaction with certain kinds of organic compounds, especially aromatic compounds. Laboratory studies with seven organic compounds (aniline. p-toluidine, phenol, 1,2,4-trihydroxybenzene, L-serine, glycine, and benzoic acid) revealed that cyanide can be formed by reaction of nitrite with some of these compounds. The most substantial free cyanide (HCN. CN-) production observed at 25 degrees C was 0.15 mg/L from reaction of 0.01 mM 1.2.4-trihydroxybenze with 5 mg/L nitrite for 72 hours. Substantial free cyanide formation was also observed at pH 2-4 in experiments with POTW effluents when reactive organics and nitrite were both added to wastewater. Formation of cyanide through nitrosation was strongly pH dependent, being most significant at low pH (2 to 4) and negligible at neutral-to-high pH. This result points to nitrous acid (HNO2) as being more reactive than the dissociated NO2- ion. The reaction of these nitrite species with organics also occurs in conventional analyses for total cyanide which involve distillation under strongly acidic conditions. Sufficient sample pretreatment with sulfamic acid at the time of sampling, not at the time of analysis. is highly recommended to prevent biasing analytical measurement of total cyanide in POTW effluents.