Environmental application of gamma technology: Update on the Canadian sludge irradiator

Waste treatment and disposal technologies have recently been subjected to increasing public and regulatory scrutiny. Concern for the environment and a heightened awareness of potential health hazards that could result from insufficient or inappropriate waste handling methods have combined to push waste generators in their search for new treatment alternatives. Gamma technology can offer a new option for the treatment of potentially infectious wastes, including municipal sewage sludge.

Sewage sludge contains beneficial plant nutrients and a high organic component that make it ideal as a soil conditioning agent or fertilizer bulking material. It also carries potentially infectious microorganisms which limit opportunities for beneficial recycling of sludges. Gamma irradiation-disinfection of these sludges offers a reliable, fast and efficient method for safe sludge recycling.

Nordion International's Market Development Division was created in 1987 as part of a broad corporate reorganization. It was given an exclusive mandate to develop new applications of gamma irradiation technology and markets for these new applications. Nordion has since explored and developed opportunities in food irradiation, pharmaceutical/cosmetic products irradiation, biomedical waste sterilization, airline waste disinfection, and sludge disinfection for recycling. This paper focuses on the last of these -a proposed sludge recycling facility that incorporates a cobalt 60 sludge irradiator.     

Multi‐residue method for the analysis of pharmaceutical compounds in sewage sludge,compost and sediments by sonication‐assisted extraction and LC determination

A method for the simultaneous determination of 16 pharmaceutical compounds in three types of sewage sludge (primary, secondary and anaerobically digested dehydrated sludge), compost and sediment samples is described. Pharmaceutical compounds evaluated were nonsteroidal anti‐inflammatory drugs (acetaminophen, diclofenac, ibuprofen, ketoprofen, naproxen and salicylic acid), antibiotics (sulfamethoxazole and trimethoprim), an anti‐epileptic drug (carbamazepine), a β‐blocker (propranolol), a nervous stimulant (caffeine), estrogens (17α‐ethinylestradiol, 17β‐estradiol, estriol and estrone) and lipid regulators (clofibric acid, metabolite of clofibrate and gemfibrozil). The method is based on the ultrasonic‐assisted extraction, clean‐up by SPE and analytical determination by HPLC with diode array and fluorescence detectors. The best extraction recoveries were achieved in a three‐step extraction procedure with methanol and acetone as extraction solvents. Extraction recoveries of several pharmaceutical compounds as caffeine were highly dependent on the type of sample evaluated. The applicability of the method was tested by analyzing primary, secondary and anaerobically digested dehydrated sludge, compost and sediment samples from Seville (Southern Spain). Ten of the sixteen pharmaceutical compounds were detected in sludge samples and five in compost and sediment samples. The highest concentration levels were recorded for ibuprofen in sewage samples, whereas salicylic acid and 17α‐ethinylestradiol were detected in all of the samples analyzed.     

Feasibility of 2,4,6-Trichlorophenol and Malonic Acid as Metabolic Uncoupler for Sludge Reduction in the Sequence Batch Reactor for Treating Organic Wastewater

The activated sludge process generates a large amount of excess sludge as a byproduct, which is one of the most serious challenges in biological wastewater treatment. In the present study, the feasibility of 2,4,6-trichlorophenol (TCP) and malonic acid (MA) as metabolic uncouplers to reduce sludge generation in the sequence batch reactor (SBR) for treating organic wastewater for a long period was studied. The results showed that 2 mg/L TCP could reduce sludge generation by about 47%, while chemical oxygen demand (COD) removal efficiency and sludge settlability were not obviously influenced. Although 10 mg/L MA could also reduce excess sludge production by about 30% while slightly affecting COD removal, it seriously deteriorated sludge settlability. Accordingly, TCP is a better uncoupler for sludge reduction for a longer period in the SBR for treating organic wastewater, and MA can only be used as a short-term or transitional uncoupler. Microscopic and 16S ribosomal deoxyribonucleic acid analyses showed that the microbial population of sludge varied when uncouplers were fed to the activated sludge system. Occurrence of large amounts of filament and the disappearance of protozoa may be the main reason for the aggravation of sludge settlability under uncoupled metabolic conditions caused by MA.     

Selected drugs in solid matrices: a review of environmental determination, occurrence and properties of principal substances

After intake, drugs absorbed by human or animal organisms are subject to metabolic reactions, such as hydroxylation, cleavage or glucuronation. However, a significant amount of the original or the metabolized substance leaves the organism via urine or feces. Thanks to improvements in analytical chemistry, many pharmaceutical compounds and endocrine disrupters are more easily detected in the surface-water and waste-water environmental compartments, at ppb concentrations.But what contaminates our solid environmental matrices? These substances can be eliminated by sorption or biodegradation but, at present, there is not enough data to allow evaluation of the behavior of the substances through the solid compartment, such as soil, sludge and bio-waste.This article provides an overview of the occurrence of pharmaceutical compounds in solid matrices on the basis of the quantities used, their physico-chemical properties and data from literature indicating the potential of the drug to persist in sediment, soil or sludge.     

Determination of nonylphenol and nonylphenol ethoxylates in wastewater using MEKC

Nonylphenol ethoxylates (NPEO_x) are surfactants which are used worldwide and can be transformed in the environment by microorganisms to form nonylphenol (NP). Analysis of these compounds was carried out with micellar electrokinetic capillary chromatography (MEKC). Different parameters such as background electrolyte (BGE) solution, pH, type of surfactant, and sample stacking were optimized. The use of CHES (20 mM, pH 9.1) in combination with 50 mM sodium cholate as a surfactant as BGE solution, together with sample stacking using 50 mM NaCl in the sample and an injection time of 20 s, provided the best separation of the compounds studied. The method was applied to the determination of target analytes in two types of sludge water coming from two steps of a wastewater treatment plant. Liquid–liquid extraction was carried out using toluene as solvent, resulting in recoveries around 100% for all studied analytes. The presence of NPEO_x was observed in the first step of the sludge water treatment, based on migration time and UV spectra. Identification was confirmed using tandem MS. LOQs of the studied compounds were in the range of 12.7 to 30.8 ng/mL, which is satisfactory for the analysis of real wastewater samples.     

Determination of chiral pharmaceuticals and illicit drugs in wastewater and sludge using microwave assisted extraction,solid-phase extraction and chiral liquid chromatography coupled with tandem mass spectrometry

This is the first study presenting a multi-residue method allowing for comprehensive analysis of several chiral pharmacologically active compounds (cPACs) including beta-blockers, antidepressants and amphetamines in wastewater and digested sludge at the enantiomeric level. Analysis of both the liquid and solid matrices within wastewater treatment is crucial to being able to carry out mass balance within these systems. The method developed comprises filtration, microwave assisted extraction and solid phase extraction followed by chiral liquid chromatography coupled with tandem mass spectrometry to analyse the enantiomers of 18 compounds within all three matrices. The method was successfully validated for 10 compounds within all three matrices (amphetamine, methamphetamine, MDMA, MDA, venlafaxine, desmethylvenlafaxine, citalopram, metoprolol, propranolol and sotalol), 7 compounds validated for the liquid matrices only (mirtazapine, salbutamol, fluoxetine, desmethylcitalopram, atenolol, ephedrine and pseudoephedrine) and 1 compound (alprenolol) passing the criteria for solid samples only. The method was then applied to wastewater samples; cPACs were found at concentration ranges in liquid matrices of: 1.7 ng L⁻¹ (metoprolol) – 1321 ng L⁻¹ (tramadol) in influent, <LOD (desmethylcitalopram and metoprolol) – 506 ng L⁻¹ in effluent, and in solid matrix digested sludge: 0.4 ng g⁻¹ (metoprolol) – 275 ng g⁻¹ (citalopram). Enantiomeric profiling revealed that studied compounds were present in analysed samples in non-racemic composition. Furthermore, enantiomeric composition of studied analytes differed in liquid and solid matrices. This demonstrates that not analysing the solid fraction of wastewater may lead to over-estimation of the removal rates of cPACs as well as possible misrepresentation of the enantiomeric fraction of the compounds as they leave the wastewater treatment plant. Consequently risks from cPACs entering the environment might be higher than anticipated.     

Analysis of perfluorinated chemicals in sludge: Method development and initial results

A fast, rigorous method was developed to maximize the extraction efficacy for ten perfluorocarboxylic acids and perfluorooctanesulfonate from waste-water-treatment sludge and to quantitate using liquid chromatography, tandem-mass spectrometry (LC/MS/MS). First, organic solvents were tested for extraction efficiency, including acetonitrile (ACN), methanol (MeOH), isopropanol (IPA), tetrahydrofuran (THF), and 50/50 ACN/MeOH (v/v). Among the extractants tested, 50/50 ACN/MeOH yielded the best results for our combined criteria of extraction efficacy and solvent-handling convenience. Second, chemical pretreatment prior to solvent extraction was tested with sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrochloric acid (HCl), and potassium persulfate (K₂S₂O₈). Pretreatment with NaOH and HCl effectively recovered additional PFCs from the sludge, but KOH and K₂S₂O₈ digestion were less effective than no pretreatment. Third, cleanup methods were investigated with solid-phase extraction using HLB (hydrophilic–lipophilic balanced) and WAX (weak-anion exchange) stationary phases, and with ion-pairing. The HLB stationary phase yielded a slight edge over the other two cleanup strategies in terms of recoverable PFCs and chromatographic separation. Finally, the appropriateness of isotopically labeled PFCs for quantitating unlabeled PFCs using isotopic dilution in complex sludge extracts was evaluated by comparison to results obtained with the standard-addition method. A National Institute of Standards and Technology (NIST) domestic sludge (CRM 2781) was analyzed using our finalized method and compared with previously reported results.     

Comparison of Methods for the Preparation of Sewage Sludge Samples Prior to the Spectrophotometric Determination of Phosphorus

Abstract

Three procedures for the preparation of sewage sludge samples prior to the colorimetric determination of phosphorus as “molybdenum blue” were evaluated. Using samples of the US EPA's municipal digested sludge as a reference material, sulfuric acid/ammonium persulfate digestion, muffle furnace ignition followed by extraction of the ash with hydrochloric acid, and direct extraction of the sewage sludge with sodium bicarbonate solution were compared in terms of phosphorus recovery as determined by colorimetric measurements. On the basisof phosphorus recovery, the samples prepared by muffle furnace ignition/hydrochloric acid extraction of the ash showed the best accuracy and precision. This procedure was also superior in terms of the time and effort expended in the preparation of the sewage sludge samples.     

Optimization of pressurized liquid extraction and purification conditions for gas chromatography-mass spectrometry determination of UV filters in sludge

This work presents an effective sample preparation method for the determination of eight UV filter compounds, belonging to different chemical classes, in freeze-dried sludge samples. Pressurized liquid extraction (PLE) and gas chromatography-mass spectrometry (GC-MS) were selected as extraction and determination techniques, respectively. Normal-phase, reversed-phase and anionic exchange materials were tested as clean-up sorbents to reduce the complexity of raw PLE extracts. Under final working conditions, graphitized carbon (0.5 g) was used as in-cell purification sorbent for the retention of co-extracted pigments. Thereafter, a solid-phase extraction cartridge, containing 0.5 g of primary secondary amine (PSA) bonded silica, was employed for off-line removal of other interferences, mainly fatty acids, overlapping the chromatographic peaks of some UV filters. Extractions were performed with a n-hexane:dichloromethane (80:20, v:v) solution at 75°C, using a single extraction cycle of 5 min at 1500 psi. Flush volume and purge time were set at 100% and 2 min, respectively. Considering 0.5 g of sample and 1 mL as the final volume of the purified extract, the developed method provided recoveries between 73% and 112%, with limits of quantification (LOQs) from 17 to 61 ng g(-1) and a linear response range up to 10 μg g(-1). Total solvent consumption remained around 30 mL per sample. The analysis of non-spiked samples confirmed the sorption of significant amounts of several UV filters in sludge with average concentrations above 0.6 μg g(-1) for 3-(4-methylbenzylidene) camphor (4-MBC), 2-ethylhexyl-p-methoxycinnamate (EHMC) and octocrylene (OC).     

Using natural 15N abundances to trace the fate of waste-derived nitrogen in forest ecosystems: New Zealand case studies

Treatment of wastewater generally results in elevated natural ¹⁵N abundance (δ¹⁵N) in the effluent and sludges. For example, high δ¹⁵N values are found in treated sewage effluent, biosolids, and other wastes that are commonly applied to land. In contrast, N deficient coniferous forest soils usually have a low δ¹⁵N. When wastes with high δ¹⁵N values are applied to land, their distinctive δ¹⁵N signature can potentially be used to trace the fate of waste-derived N in the ecosystem. In this paper, we provide an overview of the use of δ¹⁵N in land application of wastes, including New Zealand case studies on tracing nitrogen in forest ecosystems.