Martin Reinhard

Impacts of emerging organic contaminants on freshwater resources: Review of recent occurrences, sources, fate and effects

Rapid urbanization and frequent disposal of wastewater to surface water cause widespread contamination of freshwater supplies with emerging contaminants, such as pharmaceuticals, insecticides, surfactants, endocrine disruptors, including hormones. Although these organic contaminants may be present at trace levels, their adverse effects on aquatic life, animals and even humans are a growing concern. Numerous studies have been published on the occurrence and fate of emerging organic contaminants in different parts of the world, spanning a wide range of sources and aquatic environments including freshwater catchments, effluent wastewater streams, lakes, rivers, reservoirs, estuaries and marine waters. This paper reviews recent studies on the occurrence and fate of frequently detected pharmaceuticals and hormones and identifies areas that merit further research.

Desorption of halogenated organics from model solids, sediments, and soil under unsaturated conditions; 1; isotherms

Desorption isotherms spanning 4-5 orders of magnitude in vapor concentration were measured for chloroform, trichloroethylene, and .tetrachloroethylene under unsaturated conditions at 100 % relative humidity. The mechanisms affecting isotherm shape were investigated using model solids, aquifer materials, and soil spanning a range in physical properties. Uptake from the vapor phase was examined in terms of four sorption mechanisms: (1) mineral surface adsorption, (2) partitioning into natural organic matter, (3) partitioning into surface-bound water, and (4) adsorption in micropores. Evidence is presented that a heretofore overlooked mechanism-adsorption in micropores-contributes significantly to sorbate uptake and contributes to isotherm nonlinearity on solids with low natural organic matter contents. Micropores are those pores less than several adsorbate diameters in width and are implicated as showing enhanced adsorption as compared to pores of larger dimension. Isotherm shape on solids with low natural organic matter appears to be dominated by intraaggregate microporosity.

Photodegradation of common environmental pharmaceuticals and estrogens in river water.

Photodegradation rates of five pharmaceuticals (gemfibrozil, ibuprofen, ketoprofen, naproxen, and propranolol) and of four estrogens (estriol, estrone [E1], 17beta-estradiol [E2], and 17alpha-ethinylestradiol [EE2]), which are common contaminants in the aquatic environment, were measured in both purified and river water at environmentally relevant concentrations (1-2 microg/L) and different oxygen concentrations. Solutions were irradiated with a xenon arc lamp (765 W/m2; 290 nm < lambda < 700 nm) and analyzed using a high-performance liquid chromatography-tandem mass spectrometry method with electrospray ionization for pharmaceuticals and atmospheric pressure photoionization for estrogens. In river water, half-lives were 4.1 min [corrected] for ketoprofen, 1.1 h [corrected] for propranolol, 1.4 h for naproxen, 2 to 3 h for estrogens, and 15 h for gemfibrozil and ibuprofen. In air-saturated purified water, rates generally were slower except for that of ketoprofen, which reacted with a half-life of 2.5 min. Naproxen, propranolol, and E1 reacted with half-lives of 1.9, 4.4, and 4.7 h, respectively. The EE2, estriol, E2, gemfibrozil, and ibuprofen reacted with half-lives of 28.4, 38.2, 41.7, 91.4, and 205 h, respectively. The presence of oxygen doubled the direct photolysis rates of naproxen and propranolol. In nonautoclaved river water, 80% of E2 rapidly biotransformed to E1 within less than 20 min, whereas all other compounds remained stable over 22 h.

Degradation of polyamide nanofiltration and reverse osmosis membranes by hypochlorite.

The degradation of polyamide (PA) nanofiltration and reverse osmosis membranes by chlorine needs to be understood in order to develop chlorine-resistant membranes. Coated and uncoated fully aromatic (FA) and piperazine (PIP) semi-aromatic PA membranes were treated with hypochlorite solution and analyzed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR). XPS results showed that in chlorine treated FA PA membranes the ratio of bound chlorine to surface nitrogen was 1:1 whereas it was only 1:6 in the case of PIP PA membranes. Surface oxygen of uncoated FA and PIP membranes increased with increasing hypochlorite concentration whereas it decreased for coated FA membranes. High resolution XPS data support that chlorination increased the number of carboxylic groups on the PA surface, which appear to form by hydrolysis of the amide bonds (C(O)-N). FTIR data indicated the disappearance of the amide II band (1541 cm(-1)) and aromatic amide peak (1609 cm(-1)) in both coated and uncoated chlorinated FA membranes, consistent with the N-chlorination suggested by the XPS results. Furthermore, the surface charge of chlorinated membranes at low pH (<6) became negative, consistent with amide-nitrogen chlorination. Chlorination appeared to both increase and decrease membrane hydrophobicity depending on chlorination exposure conditions, which implied that N-chlorination and hydrolysis may be competing processes. The effects of property changes on the membrane performance were also observed for NF90, BW30, and NF270 membranes.

Comparing microfiltration-reverse osmosis and soil-aquifer treatment for indirect potable reuse of water

Microfiltration (MF) followed by reverse osmosis (RO) and soil-aquifer treatment (SAT) are the two principal technologies considered for indirect potable reuse of wastewater. This study, conducted at the Northwest Water Reclamation Plant, Mesa (Arizona), evaluated MF/RO and SAT (>6 months residence time) treated tertiary effluent with respect to organics removal. Effluent organic matter was characterized as total organic carbon (TOC), by UV absorbance (UVA), solid-state carbon-13 nuclear magnetic resonance spectroscopy, and size exclusion chromatography. Several trace organic micropollutants, including EDTA, NTA, and alkylphenolethoxylate residues, were analyzed by GC/MS. The study revealed that final TOC concentrations of MF/RO and SAT are 0.3 and 1.0 mgl(-1), respectively. Based on the characterization techniques used, the character of bulk organics present in final SAT water resembles the character of natural organic matter present in drinking water. Depending on the molecular weight cut-off, RO membranes can efficiently reject high molecular weight organic matter (characterized as humic and fulvic acids). However, approximately 40-50 percent of the remaining TOC in permeates consists of low molecular weight acids and neutrals representing a molecular weight range of approximately 500Da and less. In the SAT treated effluent, EDTA and APECs were removed to approximately 4.3 and 0.54 microg/l, respectively, but were below the detection limit in the MF/RO treated effluent.

Transformation of carbon tetrachloride by pyrite in aqueous solution.

The reactivity of CCl 4 with pyrite was investigated by measuring the CCl 4 transformation rates and products under aerobic and anaerobic conditions. Under all reaction conditions, >90% of the CCl 4 was transformed within 12-36 days in the presence of 1.2-1.4 m 2 /L pyrite at 25 o C. A zero-order dependence on the CCl 4 concentration supports a surface-controlled reaction mechanism wherein the rate of reaction depends on the absorbed CCl 4 concentration

Hydrodechlorination and hydrogenation of aromatic compounds over palladium on alumina in hydrogen-saturated water

The catalytic transformations of 1,2-dichlorobenzene, chlorobenzene, 4-chlorobiphenyl, γ-hexachlorocyclohexane (Lindane), naphthalene and phenanthrene were studied over palladium on alumina in hydrogen-saturated water (Pd/Al2O3/H2) at room temperature and ambient pressure. The chlorinated benzenes were rapidly hydrodechlorinated and Lindane was dehydrochlorinated to benzene. Partial or complete hydrogenation was observed for biphenyl and the polycyclic aromatic hydrocarbons. The phenanthrene ring was cleaved at the 9,10-position. In general dechlorination reactions were faster than hydrogenation reactions.

Critical review of Pd-based catalytic treatment of priority contaminants in water

Catalytic reduction of water contaminants using palladium (Pd)-based catalysts and hydrogen gas as a reductant has been extensively studied at the bench-scale, but due to technical challenges it has only been limitedly applied at the field-scale. To motivate research that can overcome these technical challenges, this review critically analyzes the published research in the area of Pd-based catalytic reduction of priority drinking water contaminants (i.e., halogenated organics, oxyanions, and nitrosamines), and identifies key research areas that should be addressed. Specifically, the review summarizes the state of knowledge related to (1) proposed reaction pathways for important classes of contaminants, (2) rates of contaminant reduction with different catalyst formulations, (3) long-term sustainability of catalyst activity with respect to natural water foulants and regeneration strategies, and (4) technology applications. Critical barriers hindering implementation of the technology are related to catalyst activity (for some contaminants), stability, fouling, and regeneration. New developments overcoming these limitations will be needed for more extensive field-scale application of this technology.

TREATMENT OF 1,2-DIBROMO-3-CHLOROPROPANE AND NITRATE-CONTAMINATED WATER WITH ZERO-VALENT IRON OR HYDROGEN/PALLADIUM CATALYSTS

The abilities of zero-valent iron powder and hydrogen with a palladium catalyst (H2/Pd-alumina) to hydrodehalogenate 1,2-dibromo-3-chloropropane (DBCP) to propane under water treatment conditions (ambient temperature and circumneutral pH) were compared. DBCP reacted with iron powder (100–200 mesh, 36 g/l) in HEPES-buffered water (pH = 7.0) with a t12 of 2.5 min and in different groundwaters (pH = 8.2–8.7) with a t12 ranging from 41–77 min. Dissolved O2 and NO−3 slowed the transformation, whereas sulfate and nitrite had little effect. Iron removed 60 mg/l of nitrate within 14 min with nitrite as an intermediate. In 75 ml groundwater containing 22.5 mg 1% Pd-alumina catalyst under 10% H2 partial pressure, DBCP was transformed to propane within minutes. The rate in groundwater was slower by about 30% compared to Milli-Qtm water. SO2−4, NO−3, Cl− or O2 added to Milli-Q water only slightly inhibited DBCP transformation by H2/Pd-alumina, while SO2−3 had a much stronger inhibitory affect.

Occurrence and fate of pharmaceuticals and alkylphenol ethoxylate metabolites in an effluent-dominated river and wetland

The occurrence of pharmaceuticals, nonylphenol ethoxylate metabolites, and other wastewater-derived contaminants in surface waters is a potential environmental concern, especially since the discovery of contaminants with endocrine-disrupting properties. The present study investigated the discharge of emerging contaminants into the Santa Ana River (CA, USA) and their attenuation during river transport and passage through a constructed wetland. Contaminants studied included pharmaceuticals (gemfibrozil, ibuprofen, naproxen, ketoprofen, and carbamazepine) and their metabolites, hormones, the metabolites of alkylphenol polyethoxylates (APEMs), N-butyl benzenesulfonamide (NBBS), and chlorinated tris-propylphosphates (TCPPs). The APEMs included alkylphenols (APs), short-chain AP polyethoxylates (APEOs), AP polyethoxycarboxylates (APECs), and carboxylated APECs (CAPECs). In wastewater treatment plant effluent, APECs and CAPECs represented the dominant APEM fraction (1.8-18.7 microg/L), whereas APEOs and APs contributed only small amounts to the overall APEM concentrations (0.10-0.92 and < or =0.1 microg/L, respectively) except where the effluent was infiltrated into soil (5.2 microg/L). In effluents, ibuprofen and its metabolites, TCPPs, and NBBS were detected regularly (<0.5 microg/L), and the other pharmaceuticals were detected occasionally. Transport in the Santa Ana River for 11 km resulted in the significant attenuation of all contaminants, from 67% for gemfibrozil to 100% for others. Wetland treatment (residence time, 2-4 d) resulted in partial removal of ibuprofen, gemfibrozil, and TCPPs and transformed APEOs to APECs.