Exploring the detection of microcystin-LR using polar organic chemical integrative samplers (POCIS).

Polar organic chemical integrative samplers (POCIS) were used in this study to explore passive sampling for the detection of microcystin-LR (MC-LR). POCIS were deployed in triplicate for a minimum of 28 days at the inlet and outlet of a 1 km2, 4.2 km long lake in Atlantic Canada. POCIS results were compared to lake water grab sampling and followed a similar trend. Laboratory POCIS studies using lake water spiked with known MC-LR concentrations were used to estimate lake water concentrations over the deployment period by calculating POCIS sampling rate (Rs). The Rs for MC-LR in this lake water was found to be 0.045 (±0.001) and 0.041 (±0.001) L per day for initial concentrations of 0.5 and 1.0 µg L-1. Estimated MC-LR concentrations from POCIS were generally higher than grab sampling results, especially at the outlet to the lake from late September to late October. This could possibly give a better picture of MC-LR concentrations in the lake; MC-LR concentrations can fluctuate substantially over short time periods. POCIS were able to detect MC-LR in the water stream when grab sampling resulted in non-detects (i.e., below detection limit of LC-MS/MS). The use of passive sampling for MC-LR could have beneficial implications for public health and toxicity testing by lowering detection limits for this chronically and acutely toxic chemical. The correlation of aqueous MC-LR concentrations to POCIS MC-LR concentrations needs further study.

Chlorination Kinetics of 11-Nor-9-carboxy-Δ9-tetrahydrocannabinol: Effects of pH and Humic Acid.

The main psychoactive compound in marijuana, Δ9-tetrahydrocannabinol (THC), and its metabolites are emerging organic contaminants that have been detected in waste and surface waters. As legalization of marijuana for medical and recreational use continues, the effects of increased use and potency of marijuana on water and wastewater treatment processes and the environment should be considered. This study examined degradation kinetics of the main urinary metabolite of THC, 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) with chlorine. THC-COOH was rapidly removed from both deionized (DI) water at pH 5.6 ± 0.2 and Suwannee River humic acid (SRHA) at pH 5.1 ± 0.2 using low doses of chlorine (0.1 to 0.50 mg free Cl2/L), with half-lives calculated from second-order kinetics constants (k2) of 8 s for DI and 42 s for DI with SRHA. Kinetic rates increased with an increase in pH from 5 to 9 in both DI water and SRHA and no interference from phosphate was observed. The chlorination pathway of electrophilic substitution of Cl at the ortho or para position of the phenol structure of THC-COOH was confirmed by detection of monochlorinated byproduct fragmentation ions using flow injection analysis with orbitrap mass spectrometry.

Investigation into the use of cement kiln dust in high density sludge (HDS) treatment of acid mine water.

The purpose of this study was to investigate the potential to replace lime with cement kiln dust (CKD) in high density sludge (HDS) treatment of acid mine drainage (AMD). The bench-scale study used two water samples: AMD sampled from a lead-zinc mine with high concentrations of iron (Fe), zinc (Zn), and arsenic (As) (Fe/Zn-AMD) and a synthetic AMD solution (Syn-AMD) spiked with ferric sulfate (Fe2(SO4)3). Arsenic was found to be significantly reduced with CKD-HDS treatment of Fe/Zn-AMD compared to lime-HDS treatment, to concentrations below the stringent mine effluent discharge regulation of 0.10 mg As/L (i.e., 0.04 ± 0.02 mg/L). Both CKD- and lime-HDS treatment of the two AMD samples resulted in settled water Fe concentrations above the stringent discharge guideline of 0.3 mg Fe/L. CKD addition in the HDS process also resulted in high settled water turbidity, above typical discharge guidelines of 15 mg TSS/L. CKD-HDS treatment was found to result in significantly improved settled solids (i.e., sludge) quality compared to that generated in the lime-HDS process. HDS treatment with CKD resulted in 25-88% lower sludge volume indices, 2 to 9 times higher % wet solids, and 10 to 20 times higher % dry solids compared to lime addition. XRD and XPS testing indicated that CKD-HDS sludge consisted of mainly CaCO3 and SiO2 with Fe(3+) precipitates attached at particle surfaces. XRD and XPS testing of the lime-HDS generated sludge showed that it consisted of non-crystalline Fe oxides typical of sludge formed from precipitates with a high water concentration. Increased sedimentation rates were also found for CKD (1.3 cm/s) compared to lime (0.3 cm/s). The increased solids loading with CKD addition compared to lime addition in the HDS process was suggested to both promote surface complexation of metal precipitates with insoluble CKD particles and increase compression effects during Type IV sedimentation. These mechanisms collectively contributed to the reduced water content of CKD-HDS sludge. The results of this study suggest that solids loading is a significant factor in increased sludge density found with the HDS process compared to conventional lime precipitation-sedimentation.

Bench-scale study of active mine water treatment using cement kiln dust (CKD) as a neutralization agent.

The overall objective of this study was to investigate the potential impact on settled water quality of using cement kiln dust (CKD), a waste by-product, to replace quicklime in the active treatment of acidic mine water. Bench-scale experiments were conducted to evaluate the treatment performance of calcium hydroxide (Ca(OH)(2)) slurries generated using four different CKD samples compared to a control treatment with quicklime (CaO) in terms of reducing acidity and metals concentrations in acid mine drainage (AMD) samples taken from the effluent of a lead/zinc mine in Atlantic Canada. Results of the study showed that all of the CKD samples evaluated were capable of achieving greater than 97% removal of total zinc and iron. The amount of solid alkaline material required to achieve pH targets required for neutralization of the AMD was found to be higher for treatment with the CKD slurries compared to the quicklime slurry control experiments, and varied linearly with the free lime content of the CKD. The results of this study also showed that a potential benefit of treating mine water with CKD could be reduced settled sludge volumes generated in the active treatment process, and further research into the characteristics of the sludge generated from the use of CKD-generated calcium hydroxide slurries is recommended.