Organic Contaminants in Chinese Sewage Sludge: A Meta-Analysis of the Literature of the Past 30 Years.

The production of sewage sludge is increasing in China but with unsafe disposal practices, causing potential risk to human health and the environment. Using literature from the past 30 years (N = 159), we conducted a meta-analysis of organic contaminants (OCs) in Chinese sludge. Most data were available from developed and populated regions, and no data were found for Tibet. Since 1987, 35 classes of chemicals consisting of 749 individual compounds and 1 mixture have been analyzed, in which antibiotics and polycyclic aromatic hydrocarbons (PAHs) were the most targeted analytes. For 13 classes of principal OCs (defined as chemicals detected in over five studies) in sludge, the median (expressed in nanograms per gram dry weight) was the highest for phthalate esters (27 900), followed by alkylphenol polyethoxylates (12 000), synthetic musks (5800), antibiotics (4240), PAHs (3490), ultraviolet stabilizers (670), bisphenol analogs (160), organochlorine pesticides (110), polybrominated diphenyl ethers (100), pharmaceuticals (84), hormones (69), perfluorinated compounds (21), and polychlorinated biphenyls (15). Concentrations of PAHs in sludges collected between 1998 and 2012 showed a decreasing trend. Study findings suggest the need for a Chinese national sewage sludge survey to identify and regulate toxic OCs, ideally employing both targeted as well as nontargeted screening approaches.

Assessing population-level stress through glucocorticoid hormone monitoring in wastewater.

Stress is oftentimes overlooked in societies, despite its life-threatening impact. Here, we assessed the feasibility of measuring endogenous stress hormones to estimate population-level stress by wastewater-based epidemiology (WBE). Two primary glucocorticoids, cortisol and cortisone, were monitored in wastewater by liquid chromatography tandem mass spectrometry (LC-MS/MS), to assess changes in these physiological markers of stress in a student population (n = 26,000 ± 7100) on a university campus in the southwestern U.S. Daily composite samples were collected for seven consecutive days each month during the Fall (Autumn) 2017 and Spring 2018 academic semesters (n = 134). Reproducible weekly patterns were seen in stress hormone excretion, with the highest levels occurring on Mondays (124 ± 44 µg d-1 per person) and Tuesdays (127 ± 54 µg d-1 per person) and the lowest on Sundays (87 ± 32 µg d-1 per person). Stress levels on weekdays (defined by class schedules Monday-Thursday) were significantly higher than on weekends (p < 0.05). During both Fall and Spring semesters, per person stress levels of these hormones were significantly higher (p < 0.05) during the first two months of each semester, 162 ± 28 µg d-1 per person (August), 104 ± 29 µg d-1 per person (September), 180 ± 14 µg d-1 per person (January), and 114 ± 54 µg d-1 per person (February) than in the remaining measured weeks in the semester, including finals week captured in both semesters. Overall Spring semester stress levels (113 ± 45 µg d-1 per person) were significantly higher than the Fall (94 ± 42 µg d-1 per person), p < 0.01. This study is the first to demonstrate the utility of endogenous biomarkers, specifically glucocorticoid hormones, to monitor population health status (in this instance community stress) in near real-time by wastewater assessments.

Comparative meta-analysis of organic contaminants in sewage sludge from the United States and China.

Characterizing the occurrence of organic contaminants (OCs) of environmental health concern in municipal sewage sludges is essential for safe handling and disposal of these abundant materials. This meta-analysis aimed to (i) summarize the extent of studies performed on the chemical composition of sewage sludges from China and the U.S., the world's two largest chemical producers, (ii) identify chemical groups of priority concern, (iii) quantitatively compare chemical abundance in sludge between nations, (iv) determine longitudinal contaminant accumulation trends in sludge, and (v) identify data gaps with regard to OC concentrations in sludge. A literature search was conducted on concentrations of OCs in U.S. sludges produced during treatment of domestic and industrial wastewater and compared statistically to contaminant levels in Chinese sludge abstracted from a recently established database. Longitudinal trends of OC occurrence were interpreted in the context of national chemical production, usage statistics, and regulations. A total of 105 studies on OCs in U.S. sewage sludge were found, while a total of 159 had been found in China. Among 1175 OCs monitored for, 23% of all analytes had been monitored in both countries (n = 269), 41% (n = 480) in China only, and the remaining 36% (n = 426) in the U.S. only. On average, concentrations of OCs were 4.0 times higher in U.S. than in Chinese sewage sludge, with the highest detection being observed for alkylphenol ethoxylates. Data from a new binational database on toxic OCs in sewage sludges suggest and reiterates the need for additional chemical monitoring in both countries, risk assessments for emerging OCs contained in sludges destined for application on land, and stronger enforcement of sludge disposal restrictions in China, where as much as 40% of sludge is currently being dumped improperly.

High-throughput multi-residue quantification of contaminants of emerging concern in wastewaters enabled using direct injection liquid chromatography-tandem mass spectrometry.

A rapid quantitative method for 135 contaminants of emerging concern (CECs) in untreated wastewater enabled with direct injection liquid chromatography-tandem mass spectrometry is presented. All compounds were analysed within 5 min on a short biphenyl cartridge using only 10 µL of filtered sample per injection. Up to 76 compounds were monitored simultaneously during the gradient (including mostly two transitions per compound and stable isotope-labelled analogues) while yielding >10 data points per peak. Evaluation of seven solid phase extraction sorbents showed no advantage for wastewater matrix removal. Excellent linearity, range, accuracy and precision was achieved for most compounds. Matrix effects were <11 % and detection limits were <30 ng L-1 on average. Application to untreated wastewater samples from three wastewater treatment works in the UK, USA and Mexico, enabled quantification of 56 compounds. Banned and EU 'watch-list' substances are critically discussed, including pesticides, macrolide antibiotics, diclofenac, illicit drugs as well as multiple pharmaceuticals and biocides. This high-throughput method sets a new standard for the speedy and confident determination of over a hundred CECs in wastewater at the part-per-trillion level, as demonstrated by performing over 260 injections per day.

Long-term tracking of opioid consumption in two United States cities using wastewater-based epidemiology approach.

Access to near-real time opioid use data is essential to the effective management of the U.S. opioid crisis. Current narcotic data collection methods are limited by time delay and would be complimented by a rapid data acquisition technique. Use of wastewater-based epidemiology (WBE) analysis may offer access to near real-time data on opioid consumption but application in the United States has been limited. From 2015 to 2017, monthly 24-h time-weighted composite samples of municipal raw wastewater from two Midwestern U.S. cities were routinely analyzed using liquid chromatography-tandem mass spectrometry for morphine, codeine, oxycodone, heroin, fentanyl, and select opioid metabolites. Concentrations of opioids (ng/L) in raw wastewater from City 1 and 2, respectively, were: morphine (713 ±â€¯38; 306 ±â€¯29; detection frequency (DF): 100%), oxycodone (17.8 ±â€¯1.1; 78 ±â€¯6; DF: 100%), codeine (332 ±â€¯37; 100 ±â€¯27; DF: 93%), heroin (41 ±â€¯16; 9 ±â€¯11; DF: 81%), and fentanyl (1.7 ±â€¯0.2; 1.0 ±â€¯0.5; DF: 62%). Average opioid consumption rates estimated using WBE ranged between 9 and 2590 mg/day/1000 persons. Anticipated overdoses and overdose-deaths calculated from analyte concentrations in wastewater forecasted 200 opioid-related overdoses/year and 39 opioid related overdose-deaths/year across the two cities during the year 2016, which aligned well with observed coroner-reported opioid deaths. This long-term U.S. screening study of opioids in wastewater was the first to utilize wastewater epidemiological data to estimate the number of expected overdose and overdose-deaths, and to identify detectable levels of the powerful synthetic opioid fentanyl in community wastewater consistently over the course of one whole year.

Retrospective nationwide occurrence of fipronil and its degradates in U.S. wastewater and sewage sludge from 2001 - 2016.

The insecticide fipronil is under regulatory scrutiny worldwide for its toxicity to pollinators and aquatic invertebrates. We conducted the first U.S. nationwide, longitudinal study of sewage sludges for fiproles, i.e., the sum of fipronil and its major degradates (fipronil sulfone, sulfide, amide, and desulfinyl). Archived sludges (n = 109) collected in three campaigns over 15 years were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing ubiquitous fiprole occurrence (0.2-385.3 µg/kg) since 2001 and a significant increase (2.4 ±â€¯0.3 fold; p < 0.005) both from 2001 to 2006/7 and from 2001 to 2015/6, but not a significant increase from 2006/7 to 2015/6 (p = 0.275). A geospatial analysis showed fiprole levels in municipal sludges to be uncoupled from agricultural use of fipronil on cropland surrounding sampled municipalities, thus pointing to non-agricultural uses (i.e., spot-on treatment and urban pest control) as a major source of fiprole loading to wastewater. Whereas anaerobic digestion was correlated with increases in fipronil sulfide at the expense of parental fipronil (p < 0.001), total fiprole levels in sewage sludges were similar regardless of the solids treatment approach applied (p = 0.519). Treatment plant effluent available from 12 facilities in 2015/6 contained fiproles at 0.3-112.9 ng/L, exceeding the United States Environmental Protection Agency (USEPA) aquatic invertebrate life benchmark for chronic fipronil exposure (11 ng/L) in 67% of cases. Whereas the USEPA identified fipronil in sludge only recently (2015), retrospective analyses and modeling conducted here show contaminant ubiquity and nationwide increases of fiprole mass (compared to 2001 levels) in U.S. municipal sludge (1140 ±â€¯230 kg in 2015/6), and treated effluent nationwide (1970 ±â€¯390 kg in 2015/6) over the past 15 years.

Tracking narcotics consumption at a Southwestern U.S. university campus by wastewater-based epidemiology.

Wastewater-based epidemiology (WBE) was applied to estimate the consumption of twelve narcotics within a Southwestern U.S. university campus. Seven consecutive 24-hour composite raw wastewater samples (n = 80) were obtained once per month from sampling locations capturing >95% of campus-generated wastewater. Samples were analyzed for indicators of consumption of morphine, codeine, oxycodone, heroin, fentanyl, methadone, buprenorphine, amphetamine, methylphenidate, alprazolam, cocaine, and MDMA using LC-MS/MS. Eleven indicator compounds (oxycodone, codeine, norcodeine, 6-acetylmorphine, EDDP, amphetamine, alprazolam, alpha-hydroxyalprazolam, cocaine, benzoylecgonine, and MDMA) occurred at 100% detection frequency across the study, followed by morphine-3-glucuronide (98%), noroxycodone (95%), methylphenidate (90%), heroin (7%), norfentanyl (7%), and fentanyl (5%). Estimates of average narcotics consumption ranked as follows in units of mg/day/1000 persons: heroin (474 ± 32), cocaine (551 ± 49), amphetamine (256 ± 12), methylphenidate (236 ± 28), methadone (72 ± 8), oxycodone (80 ± 6), alprazolam (60 ± 2), MDMA (88 ± 35), codeine (50 ± 4), and morphine (18 ± 3). This campus-based WBE study yielded baseline data on 12 narcotics for a U.S. campus and demonstrated for the first time the feasibility of detecting the fentanyl metabolite norfentanyl in this setting.