Occurrence and risk screening of alcohol ethoxylate surfactants in three U.S. river sediments associated with wastewater treatment plants.

Alcohol ethoxylates (AE) are high production volume (HPV) chemicals globally used in detergent and personal care products and are truly a work-horse for the household and personal care industries. Commercial AE generally consist of a mixture of several homologues of varying carbon chain length and degree of ethoxylation. Homologues that are not ethoxylated are also known as aliphatic alcohols or simply fatty alcohols (FA). This group of homologues represents a special interest in the context of environmental risk, as these are also abundant and ubiquitous naturally occurring compounds (e.g. animal fats and in human feces). Hence, in a risk assessment one needs to distinguish between the natural (background) concentrations and the added contribution from anthropogenic activities. We conducted a weight-of-evidence risk assessment in three streams, documenting the exposure and predicted risk, and compared these to the habitat and in situ biota. We found that the parameters (e.g., habitat quality and total perturbations hereunder total suspended solids (TSS) and other abiotic and biotic stressors) contributed to the abundance of biota rather than the predicted risk from AE and FA. Moreover, the documented natural de novo synthesis and rapid degradation of FA highlight the need to carefully consider the procedures for environmental risk assessment of naturally occurring compounds such as FA, e.g. in line with the added risk concept known from metal risk assessment.

Relationships between benthic macroinvertebrate community structure and geospatial habitat, in-stream water chemistry, and surfactants in the effluent-dominated Trinity River, Texas, USA.

Over the past 20 years, benthic macroinvertebrate community structure studies have been conducted on the upper Trinity River, Texas, USA, which is dominated by municipal wastewater treatment plant (WWTP) and industrial effluents. The Trinity River is located in the Dallas-Fort Worth metropolitan area, and is the most highly populated and industrialized watershed in Texas. As such, the Trinity River represents a near-worst-case scenario to examine the environmental effects of domestic-municipal and industrial effluents on aquatic life. A 1987 to 1988 study concluded that many stretches of the river supported a diverse benthic community structure; however, a decline in taxa richness occurred immediately downstream of WWTPs. A 2005 study designed to parallel the 1987 to 1988 efforts evaluated how changes in water quality, habitat, and increased urbanization impacted benthic community structure. Physicochemical measurements, habitat quality, geospatial variables, and benthic macroinvertebrates were collected from 10 sites. Surfactants were measured and toxic units (TUs) were calculated for surface water and pore water as indicators of domestic/household use of cleaning products. Total TUs indicated a low potential for biological impacts. Toxic unit distribution was not dependent on WWTP location and did not correlate with any benthic variable. Eight environmental parameters were determined to be useful for predicting changes in benthic macroinvertebrate community structure: surfactant surface water TUs (SWTU), in-stream habitat cover, and surface water total organic carbon were the top three parameters. Abundance, taxa richness, and taxa similarity in 2005 had increased since the earlier study throughout the immediate vicinity of the metropolitan area.

An overview of hazard and risk assessment of the OECD high production volume chemical category--long chain alcohols [C(6)-C(22)] (LCOH).

This review summarizes the findings of the assessment report for the category, long chain alcohols (LCOH) with a carbon chain length range of C(6)-C(22) covering 30 substances, and >1.5million tonnes/year consumed globally. The category was evaluated under the Organization for Economic Co-operation and Development (OECD) high production volume chemicals program in 2006. The main findings of the assessment include: (1) no unacceptable human or environmental risks were identified; (2) these materials are rapidly and readily biodegradable; (3) a parabolic relationship was demonstrated between carbon chain length and acute and chronic aquatic toxicity; (4) category-specific (quantitative) structure-activity relationships were developed enabling prediction of properties across the entire category; (5) LCOH occur naturally in the environment in an equilibrium between synthesis and degradation; (6) industry coming together and sharing resources results in minimizing the need for additional animal tests, produces cost savings, and increases scientific quality of the assessment.

Occurrence and weight-of-evidence risk assessment of alkyl sulfates, alkyl ethoxysulfates, and linear alkylbenzene sulfonates (LAS) in river water and sediments.

Alkyl sulfates (AS), alkyl ethoxysulfates (AES) and linear alkyl benzene sulfonates (LAS) are all High Production Volume (HPV) and 'down-the-drain' chemicals used globally in detergent and personal care products, resulting in low levels ultimately released to the environment via wastewater effluent. Due to their surfactant properties, they preferentially sorb to sediments. Hence, assessment of their levels and potential perturbations on benthos are of interest. The relative levels of AS/AES decreased with distance from the wastewater treatment plant outfall. However, this was not evident for LAS. Short chained AES and especially AS dominated the homologue distribution for AES. There were no evident patterns in LAS homologue distribution. The overall mean margin of exposure (MoE) for AS/AES and LAS is approximately 40 (range: 3 to 100) suggesting no noteworthy perturbation on biota. The findings in this study are in concordance with previous preliminary hazard screening. Comparative sediment contamination analyses principally based on Chapman and Anderson [Chapman PM, Anderson, J. A decision-making framework for sediment contamination. Integr Environ Assess Mana. 2005; 1: 163-173.] and the U.S. Environmental Protection Agency RAPID assessment methods [USEPA. Rapid bioassessment protocols for use in wadeable streams and rivers: Periphyton, benthic, macroinvertebrates, and fish. 1999. Second Edition. U.S. Environmental Protection Agency Office of Water, Washington, D.C. EPA 841-B-99-002.] did not reveal significant correlations between the surfactant concentrations and ecological status of the sampling locations. Several Lines of Evidence (LoE) of the Weight-of-Evidence (WoE) lead to the conclusion of low aquatic risk associated to the monitored compounds.

Assessment of alcohol ethoxylate surfactants and fatty alcohols mixtures in river sediments and prospective risk assessment.

A feasible and relatively readily available analytical method was adapted for the assessment of alcohol ethoxylates (AE) and fatty alcohols (FA) in sediments. This study illustrates the simultaneous measurement of 38 of 114 possible alcohol ethoxylate ethoxymers (AE) and fatty alcohols (FA) found in commercially important AE products. We predicted toxicity for all identified fractions, as well as the total mixture toxicity, relative to three exposure scenarios via sewage treatment plants (STP) for these widely used chemicals in consumer products and hence generate a preliminary environmental risk screening for AE and FA in sediments. The method is based on derivatization of solvent or solid-phase extracts with 2-fluoro-N-methylpyridinium p-toluenesulfonate (Pyr+). The derivatized extracts were analyzed with liquid chromatography/mass spectrometry (LC/MS) operating in the positive ion electrospray mode. The extraction efficiency of AE and FA in three different sediments of varying composition was evaluated with spike-recovery studies, ranging from 64% to 80%. The detection limits for individual ethoxymers typically ranged from 1 to 5 ngg(-1)on a dry weight basis. The mean limit of detection (LOD) was 6 ngg(-1)and the median LOD was 3 ngg(-1). AE and FA in sediments were found to be stable for two weeks if preserved with 3% (v/v) formalin and stored at 4-6( composite function)C. Based on equilibrium partitioning, background concentrations of AE and FA were predicted to be below concentrations known to elicit chronically toxic effects. Total worst case mixture toxicities for all AE ethoxymers combined with FA were predicted to result in a risk quotient less than 0.6. Activated sludge treatment (STP) significantly reduced the release of total AE and FA by four-fold, suggesting that the total mixture risk quotient would be < 0.15 for sediment dependent organisms.

Occurrence and hazard screening of alkyl sulfates and alkyl ethoxysulfates in river sediments.

Alkyl sulfates (AS) and alkyl ethoxysulfates (AES) are High Production Volume (HPV) 'down-the-drain' chemicals widely used globally in detergent and personal care products, resulting in low levels (ng to microg L(-1) range) ultimately released to the environment via wastewater. These surfactants have a strong affinity for sorption to sediments. However, data regarding the fate and effects following release into the environment has not been reported. Sediment samples from both normal exposed and presumably low exposed locations (background) were analyzed to determine the levels of AS/AES. The method used in this study shows broad applicability across various sediment types and the most common congeners of AS/AES. The combined levels of AS/AES detected in the two presumed lower exposed sites ranged from 0.025 and 0.034 microg g(-1) on a dry weight (dw) basis while the presumed higher exposed site had combined levels of AS/AES of 0.117 microg g(-1) (dw) based on triplicate analyses. Results indicate that detectable levels of AS/AES can be found in sediments in the environment at these three sites that are below the concentrations expected to produce significant adverse ecological effects for individual homologues and the whole mixture, the hazard screening for these three sites had PEC(porewater)/PNEC(total mixture) ratios of 0.007-0.024. However, further investigation of potential effects and risk assessment is warranted.

Investigation of an onsite wastewater treatment system in sandy soil: site characterization and fate of anionic and nonionic surfactants.

This study reports on the fate of linear alkylbenzene sulfonate (LAS), alcohol ethoxylate (AE), and alcohol ether sulfate (AES) surfactants in a home septic system near Jacksonville (FL, USA) that has been used since 1976. The drainfield at this site resides in fine sand (< 6% silt and clay) with an unsaturated zone that ranges from 0 to 1.3 m. During the wettest times of the year, it is likely that effluent from the septic system passes directly into the groundwater without exposure to an unsaturated zone of soil. Groundwater was collected during two sampling events, representing seasonal high and low groundwater table levels, and analyzed for the surfactants LAS, AES, and AE. During the wet season, the unsaturated zone was approximately 0.01 m beneath the drainfield. During the dry season, the unsaturated zone was about 0.4 m below the drainfield. Alcohol ethoxylate was not detected in any groundwater samples during either sampling. Alcohol ether sulfate was not found in the dry season sampling, but traces of AES had migrated downgradient about 4.7 m horizontally and 1.8 m vertically in the wet season. Linear alkylbenzene sulfonate was detected in some dry season samples and had moved downgradient some 11.7 m horizontally and 3.7 m vertically in the wet season. These observations demonstrate that these surfactants were removed to a great extent; otherwise, they would have traveled more than 260 m downgradient, which is the calculated distance that a conservative tracer like bromide would have moved downgradient over the life of the system. The most likely removal mechanisms for these surfactants were biodegradation and sorption. Therefore, this study indicates that LAS, AE, and AES are readily removed from groundwater in soils below septic system drainfields even in situations with minimal unsaturated soil zones.

Investigation of an onsite wastewater treatment system in sandy soil: sorption and biodegradation of linear alkylbenzene sulfonate.

The objective of this work was to determine the sorptive and biodegradable characteristics of linear alkylbenzene sulfonate (LAS) in a soil below a Florida, USA, septic system drainfield. Three distinct soil samples were collected from the septic system drainfield study site. These soils were used in laboratory sorption and biodegradation studies. Different concentrations of LAS were added, in radiolabeled and unlabeled forms, to a series of test vessels that contained upgradient groundwater and the soils collected from the study site. The sorption test was designed to determine the partitioning of LAS between groundwater and soil in each sample. Results indicated that the sorption distribution coefficient (Kd) decreased from 4.02 to 0.43 L/kg and that the rate of ultimate biodegradation (first-order rate constant, k1) decreased from 2.17 to 0.08/d with increasing distance (0.7-1.2 m vertically below ground surface [BGS] and 0 to 6.1 m horizontally) from the drainfield. The three soils showed 49.8 to 83.4% LAS mineralization (percentage of theoretical CO2) over 45- or 59-d test periods. These results demonstrate that subsurface soils in this system have the potential to sorb and biodegrade LAS.

Investigation of an onsite wastewater treatment system in sandy soil: modeling the fate of surfactants.

Field monitoring data for three common laundry detergent surfactants were used to test the applicability of a mathematical model that was developed as a screening-level tool for predicting the fate and transport of consumer product ingredients in septic systems. This model takes into account the simultaneous effects of sorption and biodegradation on the transport of chemicals through a septic system. Predicted groundwater concentrations of alcohol ethoxylate (AE) and alcohol ethoxy sulfate (AES) surfactants were in excellent agreement with measured values. This good agreement was to some extent due to the fact that the biodegradation rates of AE and AES do not vary significantly as a function of the degree of oxygenation of the soil. However, using laboratory-measured soil biodegradation rates for linear alkylbenzene sulfonate (LAS), the model underpredicted measured LAS concentrations in groundwater downgradient from the drainage field. This underprediction was due to the fact that the groundwater beneath the drainage field was anoxic during certain parts of the year and LAS is not degradable under this condition. Measured LAS concentrations were consistent with an assumed in situ soil biodegradation rate that was lower than the rate measured under fully oxygenated laboratory conditions. A limitation of the model is that only one soil biodegradation rate can be input for the saturated zone, even though biodegradation rates may vary seasonally or with distance from the drainage field. However, the model was appropriate and useful as a screening tool for the sorbable organic compounds studied. The applicability of the model to other classes of compounds should be assessed before broader application.