Chronic Toxicities of Neonicotinoids to Nymphs of the Common New Zealand Mayfly Deleatidium spp.

Neonicotinoid insecticides have been shown to have high chronic toxicity relative to acute toxicity, and therefore short-term toxicity tests ≤96 h in duration may underestimate their environmental risks. Among nontarget aquatic invertebrates, insects of the orders Diptera and Ephemeroptera have been found to be the most sensitive to neonicotinoids. To undertake a more accurate assessment of the risks posed by neonicotinoids to freshwater ecosystems, more data are needed from long-term tests employing the most sensitive taxa. Using nymphs of the common New Zealand mayfly genus Deleatidium spp., we performed 28-d static-renewal exposures with the widely used neonicotinoids imidacloprid, clothianidin, and thiamethoxam. We monitored survival, immobility, impairment, and mayfly moulting propensity at varying time points throughout the experiment. Imidacloprid and clothianidin exerted strong chronic toxicity effects on Deleatidium nymphs, with 28-d median lethal concentrations (LC50s) of 0.28 and 1.36 µg/L, respectively, whereas thiamethoxam was the least toxic, with a 28-d LC50 > 4 µg/L (highest concentration tested). Mayfly moulting propensity was also negatively affected by clothianidin (during 3 of 4 wk), imidacloprid (2 of 4 wk), and thiamethoxam (1 of 4 wk). Comparisons with published neonicotinoid chronic toxicity data for other mayfly taxa and larvae of the midge genus Chironomus showed similar sensitivities for mayflies and midges, suggesting that experiments using these taxa provide reliable assessments of the threats of neonicotinoids to the most vulnerable freshwater species. Environ Toxicol Chem 2019;38:2459-2471. © 2019 SETAC.

Increased concentrations of polycyclic aromatic hydrocarbons in Alpine streams during annual snowmelt: investigating effects of sampling method, site characteristics, and meteorology.

Silicone passive samplers and macroinvertebrates were used to measure time-integrated concentrations of polycyclic aromatic hydrocarbons (PAHs) in alpine streams during annual snowmelt. The three sampling sites were located near a main highway in Arthur's Pass National Park in the Southern Alps of New Zealand. A similar set of PAH congeners, composed of 2-4 rings, were found in silicone passive samplers and macroinvertebrates. The background PAH concentrations were similar at all sites, implying that proximity to the highway did not affect concentrations. In passive samplers, an increase of PAH concentrations by up to seven times was observed during snowmelt. In macroinvertebrates, the concentration changes were moderate; however, macroinvertebrate sampling did not occur during the main pulse observed in the passive samplers. The extent of vegetation in the catchment appeared to affect the concentration patterns seen at the different stream sites. A strong correlation was found between PAH concentrations in passive samplers and the amount of rainfall in the study area, indicating that the washout of contaminants from snowpack by rainfall was an important process.

Assessing in situ rates of anaerobic hydrocarbon bioremediation.

Identifying metabolites associated with anaerobic hydrocarbon biodegradation is a reliable way to garner evidence for the intrinsic bioremediation of problem contaminants. While such metabolites have been detected at numerous sites, the in situ rates of anaerobic hydrocarbon decay remain largely unknown. Yet, realistic rate information is critical for predicting how long individual contaminants will persist and remain environmental threats. Here, single-well push-pull tests were conducted at two fuel-contaminated aquifers to determine the in situ biotransformation rates of a suite of hydrocarbons added as deuterated surrogates, including toluene-d(8), o-xylene-d(10), m-xylene-d(10), ethylbenzene-d(5) (or -d(10)), 1, 2, 4-trimethylbenzene-d(12), 1, 3, 5-trimethylbenzene-d(12), methylcyclohexane-d(14) and n-hexane-d(14). The formation of deuterated fumarate addition and downstream metabolites was quantified and found to be somewhat variable among wells in each aquifer, but generally within an order of magnitude. Deuterated metabolites formed in one aquifer at rates that ranged from 3 to 50 µg l(-1) day(-1), while the comparable rates at another aquifer were slower and ranged from 0.03 to 15 µg l(-1) day(-1). An important observation was that the deuterated hydrocarbon surrogates were metabolized in situ within hours or days at both sites, in contrast to many laboratory findings suggesting that long lag periods of weeks to months before the onset of anaerobic biodegradation are typical. It seems clear that highly reduced conditions are not detrimental to the intrinsic bioremediation of fuel-contaminated aquifers.

Determination of alkylbenzene metabolites in groundwater by solid-phase extraction and liquid chromatography-tandem mass spectrometry.

Benzylsuccinate (BSA), methylbenzylsuccinate (methylBSA), and ethylbenzylsuccinate (ethylBSA) are unambiguous anaerobic biotransformation products from toluene, xylenes, and ethylbenzene decay, respectively, and may be used to indicate intrinsic bioremediation is occurring at hydrocarbon-contaminated sites. In order to improve upon current methods that detect and quantify anaerobic hydrocarbon metabolites in field samples, solid-phase extraction (SPE) and direct sample injection methods coupled with liquid chromatography-tandem mass spectrometry (LC-MS-MS) were evaluated. In laboratory studies, recoveries of authentic standards of non-deuterated or deuterated benzylsuccinates and toluates ranged from 80 to 106% with relative standard errors ranging from 2 to 4%. The method detection limits for these analytes using SPE-LC-MS-MS ranged from 0.006 to 0.029 microg/L whereas those for direct injection-LC-MS-MS ranged from 0.61 to 1.5 microg/L. Given the increased sensitivity of using SPE coupled with LC-MS-MS, this technique was then used to analyze for the presence of putative anaerobic alkylbenzene metabolites in groundwater from a hydrocarbon-contaminated site where single-well push-pull tests were conducted using deuterated aromatic hydrocarbons. Both deuterated and non-deuterated benzylsuccinates and toluates were successfully detected and quantified in field samples using this method.