Bioaccumulation surveillance in Milford Haven Waterway

Biomonitoring of contaminants (metals, organotins, polyaromatic hydrocarbons (PAHs), PCBs) was undertaken in Milford Haven Waterway (MHW) and a reference site in the Tywi Estuary (St Ishmael/Ferryside) during 2007–2008. Bioindicator species encompassed various uptake routes—Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Hediste (=Nereis) diversicolor (sediments). Differences in feeding and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant burdens in MHW were higher than the Tywi reference site, reflecting inputs. Elevated metal concentrations were observed at some MHW sites, whilst As and Se (molluscs and seaweed) were consistently at the higher end of the UK range. However, for most metals, distributions in MH biota were not exceptional. Several metal-species combinations indicated increases in bioavailability upstream, which may reflect the influence of geogenic/land-based sources—perhaps enhanced by lower salinity. TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in M. edulis, whereas some H. diversicolor populations appear subjected to localized (historical) sources. PAHs in H. diversicolor were distributed evenly across most of MHW, although acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene were highest at one site near the mouth; naphthalenes in H. diversicolor were enriched in the mid-upper Haven (a pattern seen in M. edulis for most PAHs). Whilst PAH (and PCB) concentrations in MH mussels were mostly above reference and OSPAR backgrounds, they are unlikely to exceed ecotoxicological thresholds. Bivalve Condition indices (CI) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream—giving rise to several significant (negative) relationships between CI and body burdens. Despite the possible influence of salinity gradient as a complicating factor, multivariate analysis indicated that a combination of contaminants could influence the pattern in condition (and the biomarkers metallothionein and TOSC). Integrating bioaccumulation data with biological and biochemical endpoints is seen as a useful way to discriminate environmental quality of moderately contaminated areas such as MHW and to prioritise cause and effect investigations.     

Occupational and environmental aerosol exposure assessment: a scientific journey from the past, through the present and into the future

This paper reviews how aerosol exposure assessment, for people in both working and living environments, has evolved over the years. It charts the main scientific developments that led to progressively improved ways of thinking and methods to assess exposure to airborne particulate matter in a manner more relevant to human health. It has been a long scientific journey as one generation of pioneering contributors has handed off to the next. In the process a consistent rationale has emerged, producing aerosol sampling criteria--and in turn exposure standards--which have been increasingly relevant to actual human exposures. The journey continues as a new generation of scientists steps up to deal with the new challenges that are emerging. An appreciation of the history of what went before is essential to charting the most effective path looking forward.     

Preparation, certification and interlaboratory analysis of workplace air filters spiked with high-fired beryllium oxide

Occupational sampling and analysis for multiple elements is generally approached using various approved methods from authoritative government sources such as the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA), as well as consensus standards bodies such as ASTM International. The constituents of a sample can exist as unidentified compounds requiring sample preparation to be chosen appropriately, as in the case of beryllium in the form of beryllium oxide (BeO). An interlaboratory study was performed to collect analytical data from volunteer laboratories to examine the effectiveness of methods currently in use for preparation and analysis of samples containing calcined BeO powder. NIST SRM(?) 1877 high-fired BeO powder (1100 to 1200 °C calcining temperature; count median primary particle diameter 0.12 μm) was used to spike air filter media as a representative form of beryllium particulate matter present in workplace sampling that is known to be resistant to dissolution. The BeO powder standard reference material was gravimetrically prepared in a suspension and deposited onto 37 mm mixed cellulose ester air filters at five different levels between 0.5 μg and 25 μg of Be (as BeO). Sample sets consisting of five BeO-spiked filters (in duplicate) and two blank filters, for a total of twelve unique air filter samples per set, were submitted as blind samples to each of 27 participating laboratories. Participants were instructed to follow their current process for sample preparation and utilize their normal analytical methods for processing samples containing substances of this nature. Laboratories using more than one sample preparation and analysis method were provided with more than one sample set. Results from 34 data sets ultimately received from the 27 volunteer laboratories were subjected to applicable statistical analyses. The observed performance data show that sample preparations using nitric acid alone, or combinations of nitric and hydrochloric acids, are not effective for complete extraction of Be from the SRM 1877 refractory BeO particulate matter spiked on air filters; but that effective recovery can be achieved by using sample preparation procedures utilizing either sulfuric or hydrofluoric acid, or by using methodologies involving ammonium bifluoride with heating. Laboratories responsible for quantitative determination of Be in workplace samples that may contain high-fired BeO should use quality assurance schemes that include BeO-spiked sampling media, rather than solely media spiked with soluble Be compounds, and should ensure that methods capable of quantitative digestion of Be from the actual material present are used.     

Trace element concentrations in surface estuarine and marine sediments along the Mississippi Gulf Coast following Hurricane Katrina

Hurricanes are relatively frequent ecological disturbances that may cause potentially long-term impacts to the coastal environment. Hurricane Katrina hit the Mississippi Gulf Coast in August 2005, and caused a storm surge with the potential to change the trace element content of coastal surface sediments. In this study, surface estuarine and marine sediments were collected monthly following the storm from ten sites along the Mississippi Gulf Coast (Mobile Bay, Grand Bay Bayous Heron and Cumbest, Pascagoula, Ocean Springs, Biloxi Gulf, Back Biloxi Bay, Gulfport Gulf, Gulfport Courthouse Rd, and Gulfport Marina). Concentrations of V, Cr, Mn, Fe, Co, Ni, Zn, As, Cd, and Pb were measured by inductively coupled plasma–mass spectrometry to evaluate their temporal and spatial variations in the year following Hurricane Katrina. Sediments were characterized by pH, particle size distribution and total carbon and nitrogen content. Trace element contents of the sediments were determined in both <2 mm and <63 μm grain size fractions. Results revealed no significant temporal and spatial variability in trace element concentrations, in either size fraction. Potential ecological risk of the sediments was assessed by using NOAA SQuiRTs’ guideline values; most concentrations remained below probable adverse effects guidelines to marine organisms suggesting that trace elements redistributed by Hurricane Katrina would not cause an adverse impact on resident organisms. Instead, the concentrations of trace elements were site-dependent, with specific contaminants relating to the use of the area prior to Hurricane Katrina.     

Effects of aqueous suspensions of titanium dioxide nanoparticles on Artemia salina: assessment of nanoparticle aggregation, accumulation, and toxicity

Aquatic stability and impact of titanium dioxide nanoparticles (TiO₂ NPs, 10–30 nm) were investigated using Artemia salina. Acute exposure was conducted on nauplii (larvae) and adults in seawater in a concentration range from 10 to 100 mg/L TiO₂ NPs for 24 and 96 h. Rapid aggregation occurred in all suspensions of TiO₂ NPs to form micrometer size particles. Yet, both nauplii and adults accumulated the aggregates significantly. Average TiO₂ content in nauplii ranged from 0.47 to 3.19 and from 1.29 to 4.43 mg/g in 24 and 96 h, respectively. Accumulation in adults was higher ranging from 2.30 to 4.19 and from 4.38 to 6.20 mg/g in 24 and 96 h, respectively. Phase contrast microscopy images revealed that Artemia were unable to excrete the particles. Thus, the TiO₂ aggregates filled inside the guts. No significant mortality or toxicity occurred within 24 h at any dose. Lipid peroxidation levels characterized with malondialdehyde concentrations were not statistically different from those of the controls (p?>?0.05). These results suggested that suspensions of the TiO₂ NPs were nontoxic to Artemia, most likely due to the formation of benign TiO₂ aggregates in water. In contrast, both mortality and lipid peroxidation increased in extended exposure to 96 h. Highest mortality occurred in 100 mg/L TiO₂ NP suspensions; 18 % for nauplii and 14 % for adults (LC₅₀?>?100 mg/L). These effects were attributed to the particle loading inside the guts leading to oxidative stress as a result of impaired food uptake for a long period of time.     

Water quality and health in northern Canada: stored drinking water and acute gastrointestinal illness in Labrador Inuit

One of the highest self-reported incidence rates of acute gastrointestinal illness (AGI) in the global peer-reviewed literature occurs in Inuit communities in the Canadian Arctic. This high incidence of illness could be due, in part, to the consumption of contaminated water, as many northern communities face challenges related to the quality of municipal drinking water. Furthermore, many Inuit store drinking water in containers in the home, which could increase the risk of contamination between source and point-of-use (i.e., water recontamination during storage). To examine this risk, this research characterized drinking water collection and storage practices, identified potential risk factors for water contamination between source and point-of-use, and examined possible associations between drinking water contamination and self-reported AGI in the Inuit community of Rigolet, Canada. The study included a cross-sectional census survey that captured data on types of drinking water used, household practices related to drinking water (e.g., how it was collected and stored), physical characteristics of water storage containers, and self-reported AGI. Additionally, water samples were collected from all identified drinking water containers in homes and analyzed for presence of Escherichia coli and total coliforms. Despite municipally treated tap water being available in all homes, 77.6% of households had alternative sources of drinking water stored in containers, and of these containers, 25.2% tested positive for total coliforms. The use of transfer devices and water dippers (i.e., smaller bowls or measuring cups) for the collection and retrieval of water from containers were both significantly associated with increased odds of total coliform presence in stored water (OR_{transfer device} = 3.4, 95% CI 1.2–11.7; OR_dipper = 13.4, 95% CI 3.8–47.1). Twenty-eight-day period prevalence of self-reported AGI during the month before the survey was 17.2% (95% CI 13.0–22.5), which yielded an annual incidence rate of 2.4 cases per person per year (95% CI 1.8–3.1); no water-related risk factors were significantly associated with AGI. Considering the high prevalence of, and risk factors associated with, indicator bacteria in drinking water stored in containers, potential exposure to waterborne pathogens may be minimized through interventions at the household level.     

Spatial distribution of metals within the liver acinus and their perturbation by PCB126

Animal studies show that exposure to the environmental pollutant 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) causes alterations in hepatic metals as measured in acid-digested volume-adjusted tissue. These studies lack the detail of the spatial distribution within the liver. Here we use X-ray fluorescence microscopy (XFM) to assess the spatial distribution of trace elements within liver tissue. Liver samples from male Sprague Dawley rats, treated either with vehicle or PCB126, were formalin fixed and paraffin embedded. Serial sections were prepared for traditional H&E staining or placed on silicon nitride windows for XFM. With XFM, metal gradients between the portal triad and the central vein were seen, especially with copper and iron. These gradients change with exposure to PCB126, even reverse. This is the first report of how micronutrients vary spatially within the liver and how they change in response to toxicant exposure. In addition, high concentrations of zinc clusters were discovered in the extracellular space. PCB126 treatment did not affect their presence, but did alter their elemental makeup suggesting a more general biological function. Further work is needed to properly evaluate the gradients and their alterations as well as classify the zinc clusters to determine their role in liver function and zinc homeostasis.     

Quantification of nitrogen in the liquid fraction and in vitro assessment of lysine bioavailability in the solid fraction of soybean meal hydrolysates

Soybean meal (SBM) is a product generated from the manufacture of soybean oil and has the potential for use as a source of fermentable sugars for ethanol production or as a protein source for animal feeds. Knowing the levels of nitrogen available from ammonium is a necessary element of the ethanolic fermentation process while identifying the levels of essential amino acids such as lysine is important in determining usage as a feed source. As such the purpose of this study was to quantify total nitrogen and ammonium in the liquid fraction of hydrolyzed SBM and to evaluate total and bioavailable lysine in the solid fraction of the hydrolyzed SBM. The effects of acid concentration, cellulase and β-glucosidase on total and ammonium nitrogen were studied with analysis indicating that higher acid concentrations increased nitrogen compounds with ammonium concentrations ranging from 0.20 to 1.24 g L^?1 while enzymatic treatments did not significantly increase nitrogen levels. Total and bioavailable lysine was quantified by use of an auxotrophic gfpmut3 E.coli whole-cell bioassay organism incapable of lysine biosynthesis. Acid and enzymatic treatments were applied with lysine bioavailability increasing from a base of 82% for untreated SBM to up to 97%. Our results demonstrated that SBM has the potential to serve in ethanolic fermentation and as an optimal source essential amino acid lysine.     

Deriving fuel-based emission factor thresholds to interpret heavy-duty vehicle roadside plume measurements

Remote sensing devices have been used for decades to measure gaseous emissions from individual vehicles at the roadside. Systems have also been developed that entrain diluted exhaust and can also measure particulate matter (PM) emissions. In 2015, the California Air Resources Board (CARB) reported that 8% of in-field diesel particulate filters (DPF) on heavy-duty (HD) vehicles were malfunctioning and emitted about 70% of total diesel PM emissions from the DPF-equipped fleet. A new high-emitter problem in the heavy-duty vehicle fleet had emerged. Roadside exhaust plume measurements reflect a snapshot of real-world operation, typically lasting several seconds. In order to relate roadside plume measurements to laboratory emission tests, we analyzed carbon dioxide (CO₂), oxides of nitrogen (NO_X), and PM emissions collected from four HD vehicles during several driving cycles on a chassis dynamometer. We examined the fuel-based emission factors corresponding to possible exceedances of emission standards as a function of vehicle power. Our analysis suggests that a typical HD vehicle will exceed the model year (MY) 2010 emission standards (of 0.2 g NO_X/bhp-hr and 0.01 g PM/bhp-hr) by three times when fuel-based emission factors are 9.3 g NO_X/kg fuel and 0.11 g PM/kg using the roadside plume measurement approach. Reported limits correspond to 99% confidence levels, which were calculated using the detection uncertainty of emissions analyzers, accuracy of vehicle power calculations, and actual emissions variability of fixed operational parameters. The PM threshold was determined for acceleration events between 0.47 and 1.4 mph/sec only, and the NO_X threshold was derived from measurements where after-treatment temperature was above 200°C. Anticipating a growing interest in real-world driving emissions, widespread implementation of roadside exhaust plume measurements as a compliment to in-use vehicle programs may benefit from expanding this analysis to a larger sample of in-use HD vehicles.

Implications: Regulatory agencies, civil society, and the public at large have a growing interest in vehicle emission compliance in the real world. Leveraging roadside plume measurements to identify vehicles with malfunctioning emission control systems is emerging as a viable new and useful method to assess in-use performance. This work proposes fuel-based emission factor thresholds for PM and NOx that signify exceedances of emission standards on a work-specific basis by analyzing real-time emissions in the laboratory. These thresholds could be used to prescreen vehicles before roadside enforcement inspection or other inquiry, enhance and further develop emission inventories, and potentially develop new requirements for heavy-duty inspection and maintenance (I/M) programs, including but not limited to identifying vehicles for further testing.