California Streams Research Articles

Characterizing benthic macroinvertebrate and algal biological condition gradient models for California wadeable Streams, USA

Abstract The Biological Condition Gradient (BCG) is a conceptual model that describes changes in aquatic communities under increasing levels of anthropogenic stress. The BCG helps decision-makers connect narrative water quality goals (e.g., maintenance of natural structure and function) to quantitative measures of ecological condition by linking index thresholds based on statistical distributions (e.g., percentiles of reference distributions) to expert descriptions of changes in biological condition along disturbance gradients. As a result, the BCG may be more meaningful to managers and the public than indices alone. To develop a BCG model, biological response to stress is divided into 6 levels of condition, represented as changes in biological structure (abundance and diversity of pollution sensitive versus tolerant taxa) and function. We developed benthic macroinvertebrate (BMI) and algal BCG models for California perennial wadeable streams to support interpretation of percentiles of reference-based thresholds for bioassessment indices (i.e., the California Stream Condition Index [CSCI] for BMI and the Algal Stream Condition Index [ASCI] for diatoms and soft-bodied algae). Two panels (one of BMI ecologists and the other of algal ecologists) each calibrated a general BCG model to California wadeable streams by first assigning taxa to specific tolerance and sensitivity attributes, and then independently assigning test samples (264 BMI and 248 algae samples) to BCG Levels 1–6. Consensus on the assignments was developed within each assemblage panel using a modified Delphi method. Panels then developed detailed narratives of changes in BMI and algal taxa that correspond to the 6 BCG levels. Consensus among experts was high, with 81% and 82% expert agreement within 0.5 units of assigned BCG level for BMIs and algae, respectively. According to both BCG models, the 10th percentiles index scores at reference sites corresponded to a BCG Level 3, suggesting that this type of threshold would protect against moderate changes in structure and function while allowing loss of some sensitive taxa. The BCG provides a framework to interpret changes in aquatic biological condition along a gradient of stress. The resulting relationship between index scores and BCG levels and narratives can help decision-makers select thresholds and communicate how these values protect aquatic life use goals.

A Case Study of Soil Moisture and Infiltration after an Urban Fire

There is an increased risk of future fire disturbances due to climate change and anthropogenic activity. These disturbances can impact soil moisture content and infiltration, which are important antecedent conditions for predicting rainfall–runoff processes in semi-arid regions. Yet these conditions are not well documented. This case study provides critical field measurements and information, which are needed to improve our understanding of mechanisms such as precipitation and temperature that lead to the variability of soil properties and processes in urban and burned landscapes. In June 2018, a fire burned a portion of the riparian zone in Alvarado Creek, an urban tributary of the San Diego River in California, United States. This fire provided an opportunity to observe soil moisture content and infiltration for one year after the fire. Three transects (one burned and two unburned) were monitored periodically to evaluate the complex spatial and temporal dynamics of soil moisture and infiltration patterns. Average dry season soil moisture content was less than five percent volume water content (%VWC) for all transects, and the burned transect exhibited the lowest %VWC during the wet season. Infiltration rates displayed a high degree of spatial and temporal variability. However, the location with the highest burn severity had the lowest average infiltration rate. The observed differences between the burned and unburned transects indicate that the fire altered hydrologic processes of the landscape and reduced the ability of the soil to retain water during the wet season. This research provides the first high-resolution soil moisture and infiltration field analysis of an urban fire-disturbed stream in southern California and a method to characterize post-fire hydrologic conditions for rainfall–runoff processes.

Two years of post-wildfire impacts on dissolved organic matter, nitrogen, and precursors of disinfection by-products in California stream waters

We investigated the effects of two California wildfires (Rocky and Wragg Fires, 2015) compared to an unburned reference watershed on water quality, dissolved organic matter (DOM), and precursors of disinfection by-products (DBPs) for two years’ post-fire. The two burned watersheds both experienced wildfires but differed in the proportion of burned watershed areas. Burned watersheds showed rapid water quality degradation from elevated levels of turbidity, color, and suspended solids, with greater degradation in the more extensively burned watershed. During the first year’s initial flushes, concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), ammonium (NH4+/NH3), and specific ultraviolet absorbance (SUVA254) were significantly higher (67 ± 40%, 418 ± 125%, 192 ± 120%, and 31 ± 17%, respectively) in the more extensively burned watershed compared to the reference watershed. These elevated values gradually declined and finally returned to levels like the reference watershed in the second year. Nitrate concentrations were near detection limits (0.01 mg-N/L) in the first year but showed a large increase in fire-impacted streams during the second rainy season, possibly due to delayed nitrification. Changes in DOM composition, especially during the initial storm events, indicated that fires can attenuate humic-like and soluble microbial by-product-like (SMP) DOM while increasing the proportion of fulvic-like, tryptophan-like, and tyrosine-like compounds. Elevated bromide (Br−) concentrations (up to 8.7 μM]) caused a shift in speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) to brominated species for extended periods (up to 2 years). Wildfire also resulted in elevated concentrations of N-nitrosodimethylamine (NDMA) precursors. Such changes in THM, HAA, and NDMA precursors following wildfires pose a potential treatability challenge for drinking water treatment, but the effects are relatively short-term (≤1 year).

Occurrence of Stimulant Drugs of Abuse in a San Diego, CA, Stream and their Consumption Rates in the Neighboring Community

Levels of amphetamine, methamphetamine, cocaine, and benzoylecgonine (BE), the metabolite of cocaine, were quantitated by solid phase extraction and liquid chromatography with tandem mass spectrometry (LC/MS/MS) in Forester Creek in San Diego County, CA, and in raw wastewater from the region’s sewage treatment plant. Drug residues in these surface waters were detected with 100% frequency. Mean concentrations were 0.022 ± 0.016, 0.450 ± 0.398, 0.024 ± 0.014, and 0.019 ± 0.012 μg/L for amphetamine, methamphetamine, BE, and cocaine respectively. Nonparametric testing by Spearman rank correlation showed significant (p < 0.05) positive correlations between the illicit drugs and traditional chemical markers (caffeine and sucralose) of sewage, with the exception of cocaine and sucralose. Because BE is a metabolite unique to human excretion, its presence in both wet and dry weather stream flows suggests a chronic and continuous condition of human sewage contamination in this urban southern California stream. Wastewater-based analysis also provided a direct way of measuring drug use within the population. Back-calculations of per-capita community drug consumption rates yielded values for amphetamine, methamphetamine and cocaine at 591, 5397, and 751 mg/d/1000 people, respectively. Notably, methamphetamine per-capita consumption rates determined in the present study for this southern California community were among the highest rates ever reported for the U.S. or Europe, and serve to confirm that methamphetamine use is surging in this area of southern California close to the USA-Mexico border.

Biofilms Provide New Insight into Pesticide Occurrence in Streams and Links to Aquatic Ecological Communities.

Streambed sediment is commonly analyzed to assess occurrence of hydrophobic pesticides and risks to aquatic communities. However, stream biofilms also have the potential to accumulate pesticides and may be consumed by aquatic organisms. To better characterize risks to aquatic life, the U.S. Geological Survey Regional Stream Quality Assessment measured 93 current-use and 3 legacy pesticides in bed sediment and biofilm from 54 small streams in California across a range of land-use settings. On average, 4 times as many current-use pesticides were detected in biofilm at a site (median of 2) as in sediment (median of 0.5). Of 31 current-use pesticides detected, 20 were detected more frequently in biofilm than in sediment and 10 with equal frequency. Pyrethroids as a class were the most potentially toxic to benthic invertebrates, and of the 9 pyrethroids detected, 7 occurred more frequently in biofilm than sediment. We constructed general additive models to investigate relations between pesticides and 6 metrics of benthic community structure. Pesticides in biofilm improved fit in 4 of the 6 models, and pesticides in sediment improved fit in 2. The results indicate that the sampling of stream biofilms can complement bed-sediment sampling by identification of more current-use pesticides present and better estimation of ecological risks.

Partial migration alters population ecology and food chain length: evidence from a salmonid fish

AbstractMany migratory species, from monarch butterflies to wildebeest, express partial migration, where only a subset of a population migrates. This intraspecific variation is likely to have large ecological consequences. We studied the ecological consequences of partial migration in a salmonid fish, Oncorhynchus mykiss, in coastal streams in California, USA. One ecotype, steelhead trout, migrates to the ocean, whereas the other, rainbow trout, completes its lifecycle in freshwater. Migration has a strong genetic basis in O. mykiss. In one stream, we found differences in the frequency of migration‐linked genotypes below and above a waterfall barrier (migratory allele frequency of 60% below vs. 31% above). Below the waterfall, in the migratory‐dominated region, the density of young fish (&lt;1 yr old) was approximately twice that in the resident‐dominated region above the waterfall (0.46 vs. 0.26 individuals/m2, respectively), presumably reflecting the higher fecundity of migratory females. Additionally, there were half as many older fish (&gt;1 yr old) in pools downstream of the waterfall (0.05 vs. 0.13 individuals/m2). In a second stream, between‐year variation in the dominance of migratory vs. resident fish allowed us to explore differences in fish density and size structure through time, and we found a consistent pattern. In brief, when migratory genotypes dominated, we found higher densities of young fish and lower densities of older fish, resulting in a simpler size structure, compared to when resident genotypes dominated. Moreover, large resident trout had a slightly higher trophic position than young fish (3.92 vs. 3.42 in one creek and 3.77 vs. 3.17 in the other), quantified with stable isotope data. The difference in fish size structure did not generate trophic cascades. Partial migration is widespread among migratory populations, as is phenotypic divergence between resident and migratory forms, suggesting the potential for widespread ecological effects arising from this common form of intraspecific variation.

Flow regimes in coastal California steelhead trout streams: Spatiotemporal patterns in magnitude, duration and timing

AbstractThe magnitude, timing and duration of precipitation events can vary considerably across spatial and temporal scales. In lotic ecosystems, such differences in precipitation patterns can strongly influence water availability, which in turn affects the population dynamics of stream biota. Connectivity flow thresholds were developed for the movement of juvenile steelhead trout using hydraulic modelling for 37 coastal California streams. Spatial patterns in magnitude, and spatiotemporal patterns in duration and timing of flows meeting threshold levels were analysed using long‐term flow gaging data. Flow thresholds for the movement of juvenile steelhead through riffle sites varied from 0.06 (San Luisito Creek, Elder Creek) to 0.82 (Redwood Creek) cms (cubic meters per second). Flow thresholds increased positively with mean bankfull width, indicating that more water is required for fish movement in wider streams. Precipitation was a dominant driver of flow duration, with flows meeting thresholds longer in wetter regions of the state when compared with drier regions. On the rising limb of the hydrograph, the onset of meeting flow thresholds was influenced by stream width, with thresholds being met earlier in wider streams when compared with narrower streams. On the receding limb of the hydrograph, flow threshold timing was influenced by precipitation, with flows remaining above the threshold later in wetter regions when compared with drier regions. Based on these findings, we recommend that the management of aquatic resources for a broad range of objectives consider regional scales that account for local patterns in precipitation, channel form and prevailing water year conditions to accommodate California's wide spatiotemporal diversity of water availability.

Using co-occurrence network topology in assessing ecological stress in benthic macroinvertebrate communities.

Ecological monitoring of streams has often focused on assessing the biotic integrity of individual benthic macroinvertebrate (BMI) communities through local measures of diversity, such as taxonomic or functional richness. However, as individual BMI communities are frequently linked by a variety of ecological processes at a regional scale, there is a need to assess biotic integrity of groups of communities at the scale of watersheds. Using 4,619 sampled communities of streambed BMIs, we investigate this question using co‐occurrence networks generated from groups of communities selected within California watersheds under different levels of stress due to upstream land use. Building on a number of arguments in theoretical ecology and network theory, we propose a framework for the assessment of the biotic integrity of watershed‐scale groupings of BMI communities using measures of their co‐occurrence network topology. We found significant correlations between stress, as described by a mean measure of upstream land use within a watershed, and topological measures of co‐occurrence networks such as network size (r = −.81, p < 10–4), connectance (r = .31, p < 10–4), mean co‐occurrence strength (r = .25, p < 10–4), degree heterogeneity (r = −.10, p < 10–4), and modularity (r = .11, p < 10–4). Using these five topological measures, we constructed a linear model of biotic integrity, here a composite of taxonomic and functional diversity known as the California Stream Condition Index, of groups of BMI communities within a watershed. This model can account for 66% of among‐watershed variation in the mean biotic integrity of communities. These observations imply a role for co‐occurrence networks in assessing the current status of biotic integrity for BMI communities, as well as their potential use in assessing other ecological communities.

In‐stream habitat and macroinvertebrate responses to riparian corridor length in rangeland streams

Conservation and restoration of riparian vegetation in agricultural landscapes has had mixed success at protecting in‐stream habitat, potentially due to the mismatch between watershed‐scale impacts and reach‐scale restoration. Prioritizing contiguous placement of small‐scale restoration interventions may effectively create larger‐scale restoration projects and improve ecological outcomes. We performed a multi‐site field study to evaluate whether greater linear length of narrow riparian tree corridors resulted in measurable benefits to in‐stream condition. We collected data at 41 sites with varying upstream tree cover nested within 13 groups in rangeland streams in coastal northern California, United States. We evaluated the effect of riparian tree corridor length on benthic macroinvertebrate communities, as well as food resources, water temperature, and substrate size. Sites with longer riparian corridors had higher percentages of invertebrates sensitive to disturbance (including clingers and EPT taxa) as well as lower water temperatures and less fine sediment, two of the most important aquatic stressors. Despite marked improvement, we found no evidence that macroinvertebrate communities fully recovered, suggesting that land use continued to constrain conditions. The restoration of long riparian corridors may be an economically viable and rapidly implementable technique to improve habitat, control sediment, and counter increasing water temperatures expected with climate change within the context of ongoing land use.

Using alpha, beta, and zeta diversity in describing the health of stream-based benthic macroinvertebrate communities.

Ecological monitoring of streams has frequently focused on measures describing the taxonomic, and sometimes functional, α diversity of benthic macroinvertebrates (BMIs) within a single sampled community. However, as many ecological processes effectively link BMI stream communities there is a need to describe groups of communities using measures of regional diversity. Here we demonstrate a role for incorporating both a traditional pairwise measure of community turnover, β diversity, in assessing community health as well as ζ diversity, a more generalized framework for describing similarity between multiple communities. Using 4,395 samples of BMI stream communities in California, we constructed a model using measures of α, β, and ζ diversity, which accounted for 71.7% of among-watershed variation in the mean health of communities, as described by the California Streams Condition Index (CSCI). We also investigated the use of ζ diversity in assessing models of stochastic vs. niche assembly across communities of BMIs within watersheds, with the niche assembly model found to be the likelier of the two.

Temporal pattern in levels of the neonicotinoid insecticide, imidacloprid, in an urban stream

Imidacloprid is a widely used insecticide with high runoff potential posing a significant threat to aquatic ecosystems. In order to determine the spatial and temporal concentrations of imidacloprid in Forester Creek, a tributary to the San Diego River, surface water samples were collected from two sites under wet-weather and dry-weather conditions. Solid phase extraction and liquid chromatography tandem mass spectrometry were utilized to quantify imidacloprid levels in all samples. Imidacloprid was detected with 100% frequency in surface water samples from Forester Creek with a median concentration of 16.9 ng/L (range: 3.8–96.8 ng/L). Over 60% of samples exceeded U.S. EPA's chronic exposure benchmark (10 ng/L). Temporal analysis displayed significantly higher levels in wet-weather than dry-weather (median 45.6 ng/L vs. 8.2 ng/L (p < 0.05)), demonstrating the influence of wet-weather runoff on stream quality. Imidacloprid generally followed a first flush pattern with the highest levels observed on the rising portion of the hydrograph as compared to the remainder of the storm, further indicating that the build-up and wash off from land surfaces during storms is a major source of imidacloprid into urban surface waters. To our knowledge, the present study is the first to document this first flush pattern for imidacloprid in an urban stream in southern California. Such data on the occurrence and levels of imidacloprid in this urban stream contribute to the limited knowledge on imidacloprid in urban environments and will promote a better understanding of sources and effects of the neonicotinoid pesticide within the southern California region.

Comparing abundance‐based and tag‐based estimates of coho salmon marine survival

AbstractObtaining reliable estimates of marine survival is essential for understanding anadromous salmon population dynamics. Two common approaches to estimating marine survival are (a) dividing abundance of returning adult salmon abundance by abundance of smolts from the same cohort, or (b) tagging a portion of the migrating smolts and estimating the return rate of tagged adults. This study compared these two approaches to estimating marine survival for coho salmon, Oncorhynchus kisutch (Walbaum), across multiple years in three California streams. Abundance‐based survival estimates were higher than tag‐based estimates; average estimates for the two techniques differed from 1.5‐fold to 7.4‐fold across streams. One likely cause for these divergent estimates is migration of juveniles from natal habitat before smolt trapping begins, resulting in an underestimate of smolt abundance and an overestimate of marine survival rate for the abundance‐based method. Estimates of marine survival obtained from abundance estimates and tag returns are not directly comparable.

The Influence of Hyporheic Exchange on Water Temperatures in a Headwater Stream

A headwater stream in coastal California was used to evaluate the temperature response of effective shade reduction. Spatial distribution of stream water temperatures for summer low-flow conditions (&lt;0.006 m3 s−1) were highly correlated with net radiation and advective heat transfers from hyporheic exchange and subsequent streambed conduction. Using a heat budget model, mean maximum stream water temperatures were predicted to increase by 1.7 to 2.2 °C for 50% and 0% effective shade scenarios, respectively, at the downstream end of a 300 m treatment reach. Effects on mean maximum stream water temperature changes, as water flowed downstream through a 500 m shaded reach below the treatment reach, were reduced by 52 to 30% from the expected maximum temperature increases under the 50% and 0% effective shade scenarios, respectively. Maximum stream water temperature change predicted by net radiation heating alone was greater than measured and heat-budget-estimated temperatures. When the influence of hyporheic water exchange was combined with net radiation predictions, predicted temperatures were similar to measured and heat-budget-predicted temperatures. Results indicate that advective heat transfers associated with hyporheic exchange can promote downstream cooling following stream water temperature increases from shade reduction in a headwater stream with cascade, step-pool, and large woody debris forced-pool morphology.

Stream macrophytes increase invertebrate production and fish habitat utilization in a California stream

AbstractStable flow and thermal regimes, coupled with geologically derived nutrients, are drivers of enhanced productivity in volcanic spring‐fed rivers. However, little information exists on biotic mechanisms or species interactions contributing to elevated productivity at higher trophic levels. In a California stream, juvenile steelhead trout were observed to preferentially select macrophyte habitat at a rate three times greater, on average, than five other habitat types. To understand the potential rearing benefits associated with macrophytes, we conducted a manipulative experiment to determine how macrophytes affect invertebrate prey availability and stream water velocity. Macrophytes supported up to nine times greater abundance of invertebrates than adjacent open gravel habitats. They also doubled invertebrate drift rates and reduced water velocity by up to 42‐fold. The results show that aquatic macrophytes are an important stream habitat feature that may be bioenergetically more favourable for rearing salmonids than more traditional lotic habitats. We suggest that macrophytes have the potential to enhance growth rates of juvenile salmonids when compared with other habitat types. Habitats that confer growth and size advantages may ultimately improve fitness and contribute to conservation of imperilled salmonids.

Obtaining Multiple Coproducts from Red Grape Pomace via Anthocyanin Extraction and Biogas Production.

Redgrape pomace (RGP), a byproduct of redwine production, is an abundant foodprocessingwaste stream in California, rich in both anthocyanins, a class of red-blue pigments, and lignocellulose. Extraction of anthocyanins and biofuel production from RGP have been investigated independently, but no research has examined employing both strategies together for maximal valorization. In this study, anthocyanins were most effectively extracted from RGP at 80 °C. Convection- and vacuum-oven drying of the pomace were found to decrease anthocyanin yield, whereas lyophilization did not significantly affect yield. Fermentable sugars were successfully separated from the crude extract via solid-phase extraction. Ionicliquid pretreatment of RGP was determined to be a nonviable option for application to anaerobic digestion. Extraction reduced biomethane output, but supplementation with the aqueous fraction of the extract mitigated much of this difference, indicating sequential extraction and fractionation of anthocyanins from RGP can minimize the impact on biofuel yields.

Dry season survival of juvenile salmonids in an intermittent coastal stream

We estimated dry season survival of imperiled salmonids in an intermittent coastal stream in California across 4 years (2009–2012). Our study encompassed two dry and two wet winters, allowing us to explore patterns of survival across and within dry seasons with different antecedent precipitation. Apparent survival of age-0+ steelhead trout (Oncorhynchus mykiss) was higher following wet winters compared with dry winters. Moreover, antecedent precipitation was positively correlated with cumulative survival of age-0+ steelhead. Within years, apparent survival of steelhead varied among weeks with a tendency to decrease in the late summer, indicating that fish exhibited some resistance to seasonal drought. Additionally, we found a slight but significant survival advantage for age-0+ coho salmon (Oncorhynchus kisutch) compared with equal-aged steelhead. Our results emphasize the influence of antecedent precipitation in driving the survival of imperiled salmonids and highlight that these fishes are somewhat resistant to seasonal drought, at least to a point.

Tools for managing hydrologic alteration on a regional scale: Setting targets to protect stream health

Abstract Widespread hydrologic alteration creates a need for tools to assess ecological impacts to streams that can be applied across large geographic scales. A regional framework for biologically based flow management can help catchment managers prioritise streams for protection, evaluate impacts of disturbance or interventions and provide a starting point for causal assessment in degraded streams. However, lack of flow data limit the ability to assess hydrologic conditions across a region. Hydrologic models can address this problem. Regionally calibrated hydrologic models were used to estimate current and reference flows at 572 bioassessment sites in southern and central coastal California. Flow alteration was characterised as the difference in 39 flow metrics calculated from simulations of present‐day and reference flow time‐series, calculated under up to four precipitation conditions. Biological condition was assessed with the California Stream Condition Index (CSCI) and its components. Logistic regressions were used to predict the likelihood of high scores (i.e. ≥10th percentile of the CSCI reference calibration data). Statistically significant relationships between increasing severity of hydrologic alteration and decreasing biological condition were used to set thresholds that reflected tolerance for risk of a stakeholder advisory group. An index of hydrologic alteration was created by selecting flow metrics based on their importance for predicting biological response variables in boosted regression tree models. Metrics were selected in the order of decreasing importance, and no more than two metrics per metric class were selected (i.e. duration, frequency, magnitude, timing and variability). Seven metrics were selected: HighDur (duration of high‐flow events), HighNum (# of high‐flow events), NoDisturb (duration between high‐ or low‐flow events), MaxMonthQ (maximum monthly discharge), Q99 (99th percentile of daily streamflow), QmaxIDR (interdecile range of annual maxima) and RBI (Richards–Baker Index). Applying the index to data from a probabilistic survey, 34% of stream‐miles in southern California were estimated to be hydrologically altered. One of four management priorities were assigned to each site based on biological condition and hydrologic status: protection (healthy and unaltered, 52% of stream‐miles), monitoring (healthy but altered 4%), evaluation of flow management (unhealthy and altered, 30%) and evaluation of other management (unhealthy but unaltered, 14%). Regionally derived biologically based targets for flow alteration allow catchment managers to prioritise activities and conduct screenings for causal assessments across large spatial scales. Furthermore, regional tools pave the way for incorporation of hydrologic management in policies and catchment planning designed to support biological integrity in streams. Development of regional tools should be a priority where hydrologic alteration is pervasive or expected to increase in response to climate change or urbanisation.

Comparisons of stable isotope (C, H, N) signatures for revealing organic matter sources and trophic relationships in headwater streams

We compared the efficacy of stable carbon, hydrogen, and nitrogen isotope ratios in identifying the resources used by insect consumers in headwater streams of southern California. We also compared gut contents with consumer stable isotope ratios and mixing model estimates of resource contributions to predator diet. Stable hydrogen isotope ratios (as δ2H) of algivores were well separated from ratios for detritivores, whereas relationships between stable carbon (as δ13C) and nitrogen (as δ15N) ratios of consumers and their expected diets were weaker and more ambiguous. δ2H values of primary consumers more strongly reflected the proportions of their gut contents consisting of algae than δ13C values. Τhe proportions of algivorous prey in predator gut contents increased with mixing model estimates of algivore contributions to predator diet using δ2H but not δ13C values. Our findings support the use of hydrogen isotope ratios in food web studies of streams in southern California and their potential use in assessing the effects of anthropogenic and natural disturbance on basal resource contributions to food webs that might not otherwise be identified using carbon isotope ratios.

Predicting Hydromodification in Streams Using Nonlinear Memory-Based Algorithms in Southern California Streams

AbstractHydromodification is a serious management concern in semiarid regions and is expected to become worse with land use and climate change. Potential stream channel responses range from increas...

Development of polyurethane-based passive samplers for ambient monitoring of urban-use insecticides in water

Widespread use of insecticides for the control of urban pests such as ants, termites, and spiders has resulted in contamination and toxicity in urban aquatic ecosystems in different regions of the world. Passive samplers are a convenient and integrative tool for in situ monitoring of trace contaminants in surface water. However, the performance of a passive sampler depends closely on its affinity for the target analytes, making passive samplers highly specific to the types of contaminants being monitored. The goal of this study was to develop a passive sampler compatible with a wide range of insecticides, including the strongly hydrophobic pyrethroids and the weakly hydrophobic fipronil and organophosphates. Of six candidate polymeric thin films, polyurethane film (PU) was identified to be the best at enriching the test compounds. The inclusion of stable isotope labeled analogs as performance reference compounds (PRCs) further allowed the use of PU film for pyrethroids under non-equilibrium conditions. The PU sampler was tested in a large aquarium with circulatory water flow, and also deployed at multiple sites in surface streams in southern California. The concentrations of pesticides derived from the PU sampler ranged from 0.5 to 18.5 ng/L, which were generally lower than the total chemical concentration measured by grab samples, suggesting that suspended particles and dissolved organic matter in water rendered them less available. The influence of suspended particles and dissolved organic matter on bioavailability was more pronounced for pyrethroids than for fipronils. The results show that the developed PU film sampler, when coupled with PRCs, may be used for rapid and sensitive in-situ monitoring of a wide range of insecticides in surface water.