Sulfamate in environmental waters.

Although sulfamate (the anion of sulfamic acid) has been in use for decades in various industrial and other applications, there is no previously published information about its occurrence and fate in environmental waters. In this study sulfamate was widely detected in environmental waters in Ontario, Canada, ranging up to 128,000ng/L. It was always detected (>100ng/L) in bulk precipitation samples and streams, it was usually detected in samples of lake water, and often detected in groundwater. Spatial and temporal variations suggest that both widespread atmospheric deposition and localized land-based anthropogenic sources of sulfamate may be important. Lower concentrations or non-detections of sulfamate in waters that had relatively low dissolved oxygen (e.g. some groundwaters) suggest that sulfamate may be degraded in the environment under suboxic or anoxic conditions. Given our findings of a wide distribution of sulfamate in environmental waters, including precipitation, it is not likely to be very useful as a wastewater tracer.

Bisphenol-A removal in various wastewater treatment processes: operational conditions, mass balance, and optimization.

Bisphenol-A (BPA) was analyzed in 499 liquid and 347 solid samples collected from twenty-five wastewater treatment plants (WWTPs) to investigate parameters affecting BPA occurrence, removal, and fate. Lagoons, chemically-assisted primary treatment, secondary treatment, and advanced treatment processes were included. Median BPA concentrations in influent and final effluent were 400 ng/L and 150 ng/L, respectively. Median removal efficiencies ranged from 1 to 77%. Respective median BPA levels in primary sludge, secondary biological sludge, and biosolids were 230, 260, and 460 ng/g with digested biosolids having the highest concentrations. The biological aerated filter and membrane bioreactor processes showed the best performance, while chemically-assisted primary treatment achieved the lowest removal. Biodegradation and sorption contributing to BPA removal were influenced by operational conditions: hydraulic retention time (HRT), solids retention time (SRT), and mixed liquor suspended solids (MLSS). The influence of HRT, SRT, and MLSS in the bioreactor was stronger during cold temperatures. In order to achieve above 80% removal, the required conditions for HRT, SRT, and MLSS were 13 h, 7 days, and 1600 mg/L during summer (median temperature 19 °C) and 13 h, 17 days, and 5300 mg/L during winter (median temperature 10 °C); indicating that longer SRT and higher MLSS were needed during winter. BPA's sorption tendency to sludge was strongly influenced by the degree of nitrification and HRT.

Occurrence and fate of four novel brominated flame retardants in wastewater treatment plants.

Four novel brominated flame retardants (NBFRs), i.e., decabromodiphenylethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB) were studied in 377 liquid samples and 288 solid samples collected from 20 wastewater treatment plants. Lagoon, primary, secondary, and advanced treatment processes were included, in order to investigate NBFR occurrence and the effects of WWTP operational conditions on NBFR removal. Median influent and effluent levels were 14 to 3,700 and 1.0 to 180 pg/L respectively, with DBDPE being the highest in both. Overall median removal efficiencies for DBDPE, BTBPE, HBB, and PBEB across all process types were 81 to 93, 76 to 98, 61 to 97, and 54 to 97 %, respectively with advanced treatment processes obtaining the best removals. NBFRs removal was related to retention time, surface loading rate, and biomass concentration. Median NBFR levels in treated biosolids were 80 to 32,000 pg/g, influenced by solids treatment processes.

Removal of pharmaceuticals and personal care products in a membrane bioreactor wastewater treatment plant.

Ninety-nine pharmaceuticals and personal care products (PPCPs) were analyzed in influent, final effluent, and biosolids samples from a wastewater treatment plant employing a membrane bioreactor (MBR). High concentrations in influent were found for acetaminophen, caffeine, metformin, 2-hydroxy-ibuprofen, paraxanthine, ibuprofen, and naproxen (10(4)-10(5) ng/L). Final effluents contained clarithromycin, metformin, atenolol, carbamazepine, and trimethoprim (>500 ng/L) at the highest concentrations, while triclosan, ciprofloxacin, norfloxacin, triclocarban, metformin, caffeine, ofloxacin, and paraxanthine were found at high concentrations in biosolids (>10(3) ng/g dry weight). PPCP removals varied from -34% to >99% and 23 PPCPs had ≥90% removal. Of the studied PPCPs, 26 compounds have been rarely or never studied in previous membrane bioreactor (MBR) investigations. The removal pathway showed that acetaminophen, 2-hydroxy-ibuprofen, naproxen, ibuprofen, codeine, metformin, enalapril, atorvastatin, caffeine, paraxanthine, and cotinine exhibited high degradation/transformation. PPCPs showing strong sorption to solids included triclocarban, triclosan, miconazole, tetracycline, 4-epitetracycline, norfloxacin, ciprofloxacin, doxycycline, paroxetine, and ofloxacin. Trimethoprim, oxycodone, clarithromycin, thiabendazole, hydrochlorothiazide, erythromycin-H2O, carbamazepine, meprobamate, and propranolol were not removed during treatment, and clarithromycin was even formed during treatment. This investigation extended our understanding of the occurrence and fate of PPCPs in an MBR process through the analysis of the largest number of compounds in an MBR study to date.

Parameters affecting the formation of perfluoroalkyl acids during wastewater treatment.

This study examined the fate and behaviour of perfluoroalkyl acids (PFAAs) in liquid and solid samples from five different wastewater treatment types: facultative and aerated lagoons, chemically assisted primary treatment, secondary aerobic biological treatment, and advanced biological nutrient removal treatment. To the best of our knowledge, this is the largest data set from a single study available in the literature to date for PFAAs monitoring study in wastewater treatment. Perfluorooctanoic acid (PFOA) was the predominant PFAA in wastewater with levels from 2.2 to 150ng/L (influent) and 1.9 to 140ng/L (effluent). Perfluorooctanesulfonic acid (PFOS) was the predominant compound in primary sludge, waste biological sludge, and treated biosolids with concentrations from 6.4 to 2900ng/g dry weight (dw), 9.7 to 8200ng/gdw, and 2.1 to 17,000ng/gdw, respectively. PFAAs were formed during wastewater treatment and it was dependant on both process temperature and treatment type; with higher rates of formation in biological wastewater treatment plants (WWTPs) operating at longer hydraulic retention times and higher temperatures. PFAA removal by sorption was influenced by different sorption tendencies; median log values of the solid-liquid distribution coefficient estimated from wastewater biological sludge and final effluent were: PFOS (3.73)>PFDA (3.68)>PFNA (3.25)>PFOA (2.49)>PFHxA (1.93). Mass balances confirmed the formation of PFAAs, low PFAA removal by sorption, and high PFAA levels in effluents.

Occurrence and fate of antibiotic, analgesic/anti-inflammatory, and antifungal compounds in five wastewater treatment processes.

The presence of pharmaceuticals and personal care products (PPCPs) in the aquatic environment as a result of wastewater effluent discharge is a concern in many countries. In order to expand our understanding on the occurrence and fate of PPCPs during wastewater treatment processes, 62 antibiotic, analgesic/anti-inflammatory, and antifungal compounds were analyzed in 72 liquid and 24 biosolid samples from six wastewater treatment plants (WWTPs) during the summer and winter seasons of 2010-2012. This is the first scientific study to compare five different wastewater treatment processes: facultative and aerated lagoons, chemically-enhanced primary treatment, secondary activated sludge, and advanced biological nutrient removal. PPCPs were detected in all WWTP influents at median concentrations of 1.5 to 92,000 ng/L, with no seasonal differences. PPCPs were also found in all final effluents at median levels ranging from 3.6 to 4,200 ng/L with higher values during winter (p<0.05). Removal efficiencies ranged between -450% and 120%, depending on the compound, WWTP type, and season. Mass balance showed that the fate of analgesic/anti-inflammatory compounds was predominantly biodegradation during biological treatment, while antibiotics and antifungal compounds were more likely to sorb to sludge. However, some PPCPs remained soluble and were detected in effluent samples. Overall, this study highlighted the occurrence and behavior of a large set of PPCPs and determined how their removal is affected by environmental/operational factors in different WWTPs.

Polybrominated diphenyl ethers in sewage sludge and treated biosolids: effect factors and mass balance.

Polybrominated diphenyl ether (PBDE) flame retardants have been consistently detected in sewage sludge and treated biosolids. Two hundred and eighty-eight samples including primary sludge (PS), waste biological sludge (WBS) and treated biosolids from fifteen wastewater treatment plants (WWTPs) in Canada were analyzed to investigate the factors affecting accumulation of PBDEs in sludge and biosolids. Factors examined included environmental/sewershed conditions and operational parameters of the WWTPs. PBDE concentrations in PS, WBS and treated biosolids were 230-82,000 ng/g, 530-8800 ng/g and 420-6000 ng/g, respectively; BDE-209,-99, and -47 were the predominant congeners. Concentrations were influenced by industrial input, leachate, and temperature. Several examinations including the measurement of BDE-202 indicated minimal debromination during wastewater treatment. Estimated solids-liquid distribution coefficients were moderately correlated to hydraulic retention time, solids loading rate, mixed liquor suspended solids, solids retention time, and removal of organic solids, indicating that PBDE partitioning to solids can be optimized by WWTPs' operational conditions. Solids treatment type strongly affected PBDE levels in biosolids: 1.5 times increase after solids digestion, therefore, digestion efficiency could be a potential factor for variability of PBDEs concentration. In contrast, alkaline treatment reduced PBDE concentrations in biosolids. Overall, mass balance approaches confirmed that PBDEs were removed from the liquid stream through partitioning to solids. Variability of PBDE levels in biosolids could result in different PBDEs burdens to agricultural land, and different exposure levels to soil organisms.

Parameters affecting the occurrence and removal of polybrominated diphenyl ethers in twenty Canadian wastewater treatment plants.

This study determined PBDE levels in influent, primary effluent, and final effluent collected from diverse treatment processes including four aerated lagoons, two facultative lagoons, four primary treatments, eight secondary biological treatments and two advanced treatments. Parameters examined for correlation included seasonal temperature, community sizes, industrial inputs, and operational conditions. PBDE levels in influent were 21-1000 ng/L (median 190 ng/L). Higher concentrations in influent samples were found during summer, and in WWTPs which treated leachate and higher proportions of industrial wastewater vs. residential wastewater. Final effluent levels ranged between 3 and 270 ng/L (median 12 ng/L). Among all congeners, the sum of BDE-209, -47 and -99 accounted for 79 and 71% of total PBDEs in influent and final effluent, respectively, with BDE-209 having the highest proportion. Median removal efficiencies for all process types exceeded 90% except primary treatment at 70%. PBDE levels and removals were correlated to the levels and removals of conventional parameters that represent wastewater strength, such as chemical oxygen demand and total suspended solids. The role of the primary clarifier was significant (∼82% removal) and removal was associated with hydraulic retention time (HRT) and surface loading rate. Best removal of PBDEs was achieved at greater than 2000 mg/L mixed liquor suspended solids (MLSS), longer than 10 h of HRT, and 9 days of solids retention time.

Stress-related gene expression changes in rainbow trout hepatocytes exposed to various municipal wastewater treatment influents and effluents.

The present study sought to examine the performance of six different wastewater treatment processes from 12 wastewater treatment plants using a toxicogenomic approach in rainbow trout hepatocytes. Freshly prepared rainbow trout hepatocytes were exposed to increasing concentrations of influent (untreated wastewaters) and effluent (C(18)) extracts for 48 h at 15 °C. A test battery of eight genes was selected to track changes in xenobiotic biotransformation, estrogenicity, heavy metal detoxification, and oxidative stress. The wastewaters were processed by six different treatment systems: facultative and aerated lagoons, activated sludge, biological aerated filter, biological nutrient removal, chemically assisted primary treated, and trickling filter/solids contact. Based on the chemical characteristics of the effluents, the treatment plants were generally effective in removing total suspended solids and chemical oxygen demand, but less so for ammonia and alkalinity. The 12 influents differed markedly with each other, which makes the comparison among treatment processes difficult. For the influents, both population size and flow rate influenced the increase in the following mRNA levels in exposed hepatocytes: metallothionein (MT), cytochrome P4503A4 (CYP3A4), and vitellogenin (VTG). Gene expression of glutathione S-transferase (GST) and the estrogen receptor (ER), were influenced only by population size in exposed cells to the influent extracts. The remaining genes-superoxide dismutase (SOD) and multidrug resistance transporter (MDR)-were not influenced by either population size or flow rate in exposed cells. It is noteworthy that the changes in MT, ER, and VTG in cells exposed to the effluents were significantly affected by the influents across the 12 cities examined. However, SOD, CYP1A1, CYP3A4, GST, and MDR gene expression were the least influenced by the incoming influents. The data also suggest that wastewater treatments involving biological or aeration processes had the best performance. We found that the effects of municipal effluents on gene expression depended on the population size, the initial properties of the incoming influent, and the wastewater treatment method applied. Considering that the long-term goals of wastewater treatment is to produce clean effluents for the aquatic biota and independent of the incoming influent, more research is needed in developing treatment processes to better protect aquatic life from anthropogenic contamination.

Distribution of antidepressant residues in wastewater and biosolids following different treatment processes by municipal wastewater treatment plants in Canada.

The fate of 14 antidepressants along with their respective N-desmethyl metabolites and the anticonvulsive drug carbamazepine (CBZ) was studied in 5 different sewage treatment plants (STPs) across Canada. Using two validated LC-MS/MS analytical methods, the concentrations of the different compounds were determined in raw influent, final effluent and treated biosolids samples. Out of the 15 compounds investigated, 13 were positively detected in most 24-h composite raw influent samples. Analysis showed that venlafaxine (VEN), its metabolite O-desmethylvenlafaxine (DVEN), citalopram (CIT), and CBZ were detected at the highest concentrations in raw influent (up to 4.3 µg L(-1) for DVEN). Cumulated results showed strong evidence that primary treatment and trickling filter/solids contact has limited capacity to remove antidepressants from sewage, while activated sludge, biological aerated filter, and biological nutrient removal processes yielded moderate results (mean removal rates: 30%). The more recalcitrant compounds to be eliminated from secondary STPs were VEN, DVEN and CBZ with mean removal rates close to 12%. Parent compounds were removed to a greater degree than their metabolites. The highest mean concentrations in treated biosolids samples were found for CIT (1033 ng g(-1)), amitriptyline (768 ng g(-1)), and VEN (833 ng g(-1)). Experimental sorption coefficients (K(d)) were also determined. The lowest K(d) values were obtained with VEN, DVEN, and CBZ (67-490 L kg(-1)). Sorption of these compounds on solids was assumed negligible (log K(d) ≤ 2). However, important sorption on solids was observed for sertraline, desmethylsertraline, paroxetine and fluoxetine (log K(d) > 4).

Distribution of estrogens, 17beta-estradiol and estrone, in Canadian municipal wastewater treatment plants.

The distribution of female hormones, 17beta-estradiol and estrone, was determined in effluents of 18 selected municipal treatment plants across Canada. Replicate 24-h composite samples were collected from the influent and final effluent of each treatment plant, and the removal efficiency compared to the operational characteristics of the plants. In conventional activated sludge and lagoon treatment systems, the mean concentrations of 17beta-estradiol and estrone in influent were 15.6 ng/l (range 2.4-26 ng/l) and 49 ng/l (19-78 ng/l). In final effluents, the mean concentrations of both 17beta-estradiol and estrone were reduced to 1.8 ng/l (0.2-14.7 ng/l) and 17 ng/l (1-96 ng/l), respectively. 17beta-estradiol was removed effectively, >75% and as high as 98%, in most of the conventional mechanical treatment systems with secondary treatment. The removal of estrone was much more complex with removal varying from 98% to situations where the concentrations in the effluent were elevated above that detected in the influent. The estrogenicity, measured using a transfected estrogen receptor in yeast (YES) assay, was also variable, ranging from high removal to elevations of estrogenicity in final effluent. Although the apparent removals were not statistically correlated with either hydraulic (HRT) or solid (SRT) retention times, plants or lagoons with high SRT were very effective at reducing the levels of hormones. Well-operated plants that achieved nitrification also tended to have higher removal of hormones than those that did not nitrify. Laboratory aerobic reactor experiments confirmed the rapid removal of 17beta-estradiol, estrone, and estrogenicity when exposed to sewage slurries.