Water soluble polymer biodegradation evaluation using standard and experimental methods.

Multiple polyethylene glycol (PEG) polymers ranging in molecular weight (MW) from 4000 to 500,000 Da, polyvinyl alcohol (PVOH) polymers with degrees of hydrolysis (DH) of 79 % and 88 % and MW 10,000 to 130,000 Da, and carboxy methyl cellulose (CMC) polymers with degrees of substitution (DS) ranging from 0.6 to 1.2 were evaluated in standard screening biodegradation tests to assess method limitations, modification potential, and reproducibility. All PEGs and PVOHs mineralized completely in OECD 301B and 302B studies reaching >80 % biodegradation with negligible dissolved organic carbon remaining at study completion. For high MW PEOs, extension of test duration was needed to reach full extent of mineralization. CMC biodegradation was directly correlated to degree of substitution with CMC 0.6 biodegrading extensively, CMC 0.79 partially biodegrading, and CMC 1.2 not biodegrading significantly in OECD 301B and 302B studies. For all materials tested in both an OECD 301B and 302B, fewer days were necessary to reach 60 % biodegradation in the OECD 302B indicating increased rates of biodegradation with higher inoculum to test chemical ratios. In a series of investigative studies using respirometry as the analytical endpoint, significant variability in the presence of competent degraders in small volume grab samples of river water was observed. Research is needed to overcome this variability and develop a standardized reproducible test method to accurately assess polymer mineralization in river water. At study completion, residual dissolved organic carbon (DOC) data confirmed respirometry data, high levels of mineralization resulted in negligible residual DOC while low levels of mineralization resulted in significant residual DOC, up to dose concentrations. DOC measurements provided confirmation of complete biodegradation when biomass incorporation and test system set up resulted in variable carbon dioxide production or oxygen demand.

Probabilistic exposure assessment of DEEDMAC using measured effluent and sludge concentrations from 41 wastewater treatment plants across the United States.

The cationic surfactant diethyldialkylester dimethyl ammonium chloride (DEEDMAC) is an active ingredient in liquid fabric softeners and, as such, is disposed of down the drain after consumer use. A monitoring program was conducted across the continental United States to measure the concentration of DEEDMAC in the effluent and sludge from 41 wastewater treatment plants (WWTPs). The concentration in the effluent ranged from 32.4 to 2660ng/L, with a mean and standard deviation of 232±450ng/L. The concentration in the sludge ranged from 0.707 to 314mg/kg dw, with a mean and standard deviation of 29.2±50mg/kg dw. The distribution of measured effluent concentrations was combined with a distribution of mixing zone dilutions factors to predict the distribution of DEEDMAC concentrations in mixing zones and sediments under mean flow and 10-year, 7 consecutive day lowest flow (7Q10 low flow) conditions. Additionally, the distribution of measured sludge concentrations was combined with a distribution of land applied sludge volumes and US tilling practices to obtain a predicted distribution of DEEDMAC concentrations in sludge amended soils. The 90th percentile concentrations of DEEDMAC in mixing zones and sediments under mean flow conditions was 10.3ng/L and 451ng/kg, respectively. The 90th percentile concentration in sludge amended soils was 1.92mg/kg. These predicted exposure concentrations were compared to published eco-toxicity data and showed that DEEDMAC has a wide margin of safety and poses negligible ecologic risk to aquatic, sediment, or terrestrial compartments.

Environmental fate of amine oxide: Using measured and predicted values to determine aquatic exposure.

Amine oxide (AO) surfactants are used widely in North American household detergents resulting in >44,000mtons disposed down the drain annually. Due to AOs substantial down the drain disposal volume, wide dispersive use, and high aquatic toxicity, there is a need to evaluate ecological exposure and corresponding risk. This study refined the current knowledge regarding the fate of AO disposed down the drain through laboratory simulation studies to evaluate biodegradation in the sewer and during activated sludge wastewater treatment. A monitoring program which measured effluent AO concentrations for the dominant carbon chain lengths, C12 and C14, at 44 wastewater treatment plants (WWTP) across the continental US was also conducted. The study results were then used as input into probabilistic exposure models to predict US receiving stream concentrations. In three separate OECD 314A Sewer Water Die-Away studies AO was rapidly biodegraded with >76% mineralized by study completion and the geometric mean of the primary biodegradation rates being 0.184h-1. Two OECD 303A Activated Sludge WWTP Simulation studies showed rapid and complete biodegradation of AO with ≤0.09% of parent AO remaining in the effluent, ≤0.03% of parent AO sorbed to sludge solids, and >97% complete mineralization of AO. Monitoring at US WWPTs confirmed low levels of AO in effluents with mean C12 and C14AO concentrations of 52.8 and 20.1ng/L respectively. Based on the monitoring data, the 90th percentile concentrations of C12 and C14AO for 7Q10 low flow stream conditions were >2 orders of magnitude lower than the predicted no effect concentrations indicating negligible aquatic risk from AO in US receiving streams. This study verifies that AO is safe for the aquatic environment even at the currently high usage volumes due to rapid biodegradation during transit through the sewer and wastewater treatment.

Assessing the biodegradability of microparticles disposed down the drain.

Microparticles made from naturally occurring materials or biodegradable plastics such as poly(3-hydroxy butyrate)-co-(3-hydroxy valerate), PHBV, are being evaluated as alternatives to microplastics in personal care product applications but limited data is available on their ultimate biodegradability (mineralization) in down the drain environmental compartments. An OECD 301B Ready Biodegradation Test was used to quantify ultimate biodegradability of microparticles made of PHBV foam, jojoba wax, beeswax, rice bran wax, stearyl stearate, blueberry seeds and walnut shells. PHBV polymer was ready biodegradable reaching 65.4 ± 4.1% evolved CO2 in 5 d and 90.5 ± 3.1% evolved CO2 in 80 d. PHBV foam microparticles (125-500 µm) were mineralized extensively with >66% CO2 evolution in 28 d and >82% CO2 evolution in 80 d. PHBV foam microparticles were mineralized at a similar rate and extent as microparticles made of jojoba wax, beeswax, rice bran wax, and stearyl stearate which reached 84.8  ± 4.8, 84.9  ± 2.2, 82.7  ± 4.7, and 86.4 ± 3.2% CO2 evolution respectively in 80 d. Blueberry seeds and walnut shells mineralized more slowly only reaching 39.3  ± 6.9 and 5.1 ± 2.8% CO2 evolution in 80 d respectively.

Probabilistic determination of the ecological risk from OTNE in aquatic and terrestrial compartments based on US-wide monitoring data.

OTNE [1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one; trade name Iso E Super] is a fragrance ingredient commonly used in consumer products which are disposed down the drain. This research measured effluent and sludge concentrations of OTNE at 44 US wastewater treatment plants (WWTP). The mean effluent and sludge concentrations were 0.69 ± 0.65 µg/L and 20.6 ± 33.8 mg/kg dw respectively. Distribution of OTNE effluent concentrations and dilution factors were used to predict surface water and sediment concentrations and distributions of OTNE sludge concentrations and loading rates were used to predict terrestrial concentrations. The 90th percentile concentration of OTNE in US WWTP mixing zones was predicted to be 0.04 and 0.85 µg/L under mean and 7Q10 low flow (lowest river flow occurring over a 7 day period every 10 years) conditions respectively. The 90th percentile sediment concentrations under mean and 7Q10 low flow conditions were predicted to be 0.081 and 1.6 mg/kg dw respectively. Based on current US sludge application practices, the 90th percentile OTNE terrestrial concentration was 1.38 mg/kg dw. The probability of OTNE concentrations being below the predicted no effect concentration (PNEC) for the aquatic and sediment compartments was greater than 99%. For the terrestrial compartment, the probability of OTNE concentrations being lower than the PNEC was 97% for current US sludge application practices. Based on the results of this study, OTNE concentrations in US WWTP effluent and sludge do not pose an ecological risk to aquatic, sediment and terrestrial organisms.

Evaluation of anionic surfactant concentrations in US effluents and probabilistic determination of their combined ecological risk in mixing zones.

Alcohol sulfates (AS), alcohol ethoxysulfates (AES), linear alkyl benzenesulfonates (LAS) and methyl ester sulfonates (MES) are anionic surfactants that are widely used in household detergents and consumer products resulting in over 1 million tons being disposed of down the drain annually in the US. A monitoring campaign was conducted which collected grab effluent samples from 44 wastewater treatment plants (WWTPs) across the US to generate statistical distributions of effluent concentrations for anionic surfactants. The mean concentrations for AS, AES, LAS and MES were 5.03±4.5, 1.95±0.7, 15.3±19, and 0.35±0.13µg/L respectively. Since each of these surfactants consist of multiple homologues that differ in their toxicity, the concentration of each homologue measured in an effluent sample was converted into a toxic unit (TU) by normalizing to the predicted no effect concentration (PNEC) derived from high tier effects data (mesocosm studies). The statistical distributions of the combined TUs in the effluents were used in combination with distributions of dilution factors for WWTP mixing zones to conduct a US-wide probabilistic risk assessment for the aquatic environment for each of the surfactants. The 90th percentile level of TUs for AS, AES, LAS and MES in mixing zones were 1.89×10-2, 2.73×10-3, 2.72×10-2, and 3.65×10-5 under 7Q10 (lowest river flow occurring over a 7day period every 10years) low flow conditions. Because these surfactants have the same toxicological mode of action, the TUs were summed and the aquatic safety for anionic surfactants as a whole was assessed. At the 90th percentile level under the conservative 7Q10 low flow conditions the forecasted TUs were 4.21×10-2 which indicates that there is a significant margin of safety for the class of anionic surfactants in US aquatic environments.

Widespread Microbial Adaptation to l-Glutamate-N,N-diacetate (L-GLDA) Following Its Market Introduction in a Consumer Cleaning Product.

l-Glutamate-N,N-diacetate (L-GLDA) was recently introduced in the United States (U.S.) market as a phosphate replacement in automatic dishwashing detergents (ADW). Prior to introduction, L-GLDA exhibited poor biodegradation in OECD 301B Ready Biodegradation Tests inoculated with sludge from U.S. wastewater treatment plants (WWTPs). However, OECD 303A Activated Sludge WWTP Simulation studies showed that with a lag period to allow for growth (40-50 days) and a solids retention time (SRT) that allows establishment of L-GLDA degraders (>15 days), significant biodegradation (>80% dissolved organic carbon removal) would occur. Corresponding to the ADW market launch, a study was undertaken to monitor changes in the ready biodegradability of L-GLDA using activated sludge samples from various U.S. WWTPs. Initially all sludge inocula showed limited biodegradation ability, but as market introduction progressed, both the rate and extent of degradation increased significantly. Within 22 months, L-GLDA was ready biodegradable using inocula from 12 WWTPs. In an OECD 303A study repeated 18 months post launch, significant and sustained carbon removal (>94%) was observed after a 29-day acclimation period. This study systematically documented field adaptation of a new consumer product chemical across a large geographic region and confirmed the ability of laboratory simulation studies to predict field adaptation.

Distributions of polycyclic musk fragrance in wastewater treatment plant (WWTP) effluents and sludges in the United States.

The polycyclic musks, AHTN and HHCB are fragrance ingredients widely used in consumer products. A monitoring campaign was conducted and collected grab effluent and sludge samples at 40 wastewater treatment plants (WWTP) across the United States to understand their occurrence and statistical distribution in these matrices. AHTN concentration in effluent ranged from <0.05 µg/L (LOQ) to 0.44 µg/L with a mean and standard deviation of 0.18 ± 0.11 µg/L. HHCB concentrations in effluent ranged from 0.45 to 4.79 µg/L with a mean of 1.86 ± 1.01 µg/L. AHTN concentrations in sludge ranged from 0.65 to 15.0mg/kg dw (dry weight) with a mean and standard deviation being 3.69 ± 2.57 mg/kg dw, while HHCB sludge concentrations were between 4.1 and 91 mg/kg with a mean of 34.0 ± 23.1mg/kg dw. Measured concentrations of AHTN and HHCB were significantly correlated with each other in both effluent and sludge. The concentrations of HHCB in both effluent and sludge were approximately an order of magnitude higher than those for AHTN, consistent with 2011 usage levels. The highest measured effluent concentrations for both AHTN and HHCB were below their respective freshwater PNECs (predicted no effect concentrations), indicating a negligible risk to biological communities below WWTPs, even in the absence of upstream dilution. Moreover, the large number of effluents and sludges sampled provides a statistical distribution of loadings that can be used to develop more extensive probabilistic exposure assessments for WWTP mixing zones and sludge amended soils.