Evaluating spectroscopic and chromatographic techniques to resolve dissolved organic matter via end member mixing analysis

Real-time or near real-time in-situ monitoring of dissolved organic matter (DOM) composition in natural waters and engineered treatment systems provides critical information to water quality scientists and engineers, particularly when the monitoring techniques can provide some information about the chemical nature of DOM. The efficacy of various indices derived from rapid, low-cost spectroscopic and chromatographic techniques to discriminate DOM composition was tested for samples prepared from well-defined mixtures of purified Aldrich humic acid (PAHA) and Suwannee River fulvic acid (SRFA). Sensitivities of the discrimination indices were examined by comparing (1) the differences between measured values and those predicted based from mass balance and the end member characteristics, and (2) the linear correlations between index values and mass ratios of the DOM mixtures. Size exclusion chromatography (SEC) results revealed that the weight-average molecular weight (MW(w)) may be a useful approach for tracking DOM mixing processes, although the number-average molecular weight (MW(n)) may be better for distinguishing different DOM compositions. Specific ultraviolet absorbance measured at 254 nm (SUVA(254)) performed better as a discrimination index than did two previously recommended absorbance ratios, both in terms of making better predictions of intermediate compositions and in exhibiting a more linear correlation with PAHA mass ratio. Several well-defined peaks in the derivative absorption spectra (301 and 314 nm for the first derivative, 217 nm for the third derivative, and 211 and 224 nm for the fourth derivative) also were found to be promising potential DOM discrimination indices. Finally, a fluorescence ratio based on humic- versus fulvic-like fluorescence proved to be a superior DOM discrimination index for the two DOM end members studied here. In general, this study illustrates the evaluation process that should be followed to develop rapid, low-cost discrimination indices to monitor DOM compositions based on end member mixing analyses.     

Effects of limiting access to prey on development of first zoeal stage of the brachyuran crabs Cancer magister and Hemigrapsus oregonensis

We tested the influence of limiting access to prey on larval development of the crabs Cancer magister and Hemigrapsus oregonensis by raising their Stage 1 larvae in the laboratory on different prey densities and with various periods of access to prey. Experiments were conducted in 1995 and 1996 at the Shannon Point Marine Center in Anacortes, Washington, USA. Our results show that crab larvae do not require continuous access to prey for optimal development nor do they appear to require light for prey capture. Survival and duration of Stage 1 C. magister fed continuously on only one-fourth the amount of the control density of prey and those fed at the control density for only 6 h per day were the same as for larvae fed continuously at the control density (20 ml⁻¹). Larvae with cyclic access to prey at the control density for 24 h and then starved for 72 h showed significantly lower survival and longer instar duration to Stage 2. Experiments on Stage 1 H. oregonensis which investigated a combination of prey density, period of access to prey and light/dark conditions during feeding revealed that survival decreased with decreasing prey density or with decreasing feeding period, but no differences were observed during periods of limited prey availability as a function of light or dark conditions. Stage duration was not affected by reduced prey density nor by the light/dark condition at the time of feeding, but it was prolonged when the period of access to prey was limited. The period of access to prey did not affect the weight of Day 1 Stage 2 larvae. Larvae fed high densities of prey for 4 h followed by 20 h of reduced-density diet exhibited the same survival and stage duration as controls that were continuously fed high-density prey. Our results define sub-optimal diets that can be used experimentally to determine the nutritional contributions made by naturally-occurring prey organisms during larval development in the two species. In nature, larvae may satisfy nutritional requirements through periodic encounters with dense prey patches during vertical migrations by day or night. Received: 12 August 1997 / Accepted: 5 February 1998     

PFAS Experts Symposium: Statements on regulatory policy,chemistry and analytics,toxicology, transport/fate,and remediation for per‐ and polyfluoroalkyl substances (PFAS) contamination issues

Sixty leading members of the scientific, engineering, regulatory, and legal communities assembled for the PFAS Experts Symposium in Arlington, Virginia on May 20 and 21, 2019 to discuss issues related to per‐ and polyfluoroalkyl substances (PFAS) based on the quickly evolving developments of PFAS regulations, chemistry and analytics, transport and fate concepts, toxicology, and remediation technologies.  The Symposium created a venue for experts with various specialized skills to provide opinions and trade perspectives on existing and new approaches to PFAS assessment and remediation in light of lessons learned managing other contaminants encountered over the past four decades. The following summarizes several consensus points developed as an outcome of the Symposium:

• Regulatory and policy issues: The response by many states and the US Environmental Protection Agency (USEPA) to media exposure and public pressure related to PFAS contamination is to relatively quickly initiate programs to regulate PFAS sites. This includes the USEPA establishing relatively low lifetime health advisory levels for PFAS in drinking water and even more stringent guidance and standards in several states. In addition, if PFAS are designated as hazardous substances at the federal level, as proposed by several Congressional bills, there could be wide‐reaching effects including listing of new Superfund sites solely for PFAS, application of stringent state standards, additional characterization and remediation at existing sites, reopening of closed sites, and cost renegotiation among PRPs.
• Chemistry and analytics: PFAS analysis is confounded by the lack of regulatory‐approved methods for most PFAS in water and all PFAS in solid media and air, interference with current water‐based analytical methods if samples contain high levels of suspended solids, and sample collection and analytical interference due to the presence of PFAS in common consumer products, sampling equipment, and laboratory materials.
• Toxicology and risk: Uncertainties remain related to human health and ecological effects for most PFAS; however, regulatory standards and guidance are being established incorporating safety factors that result in part per trillion (ppt) cleanup objectives. Given the thousands of PFAS that may be present in the environment, a more appropriate paradigm may be to develop toxicity criteria for groups of PFAS rather than individual PFAS.
• Transport and fate: The recalcitrance of many perfluoroalkyl compounds and the capability of some fluorotelomers to transform into perfluoroalkyl compounds complicate conceptual site models at many PFAS sites, particularly those involving complex mixtures, such as firefighting foams. Research is warranted to better understand the physicochemical properties and corresponding transport and fate of most PFAS, of branched and linear isomers of the same compounds, and of the interactions of PFAS with other co‐contaminants such as nonaqueous phase liquids. Many PFAS exhibit complex transport mechanisms, particularly at the air/water interface, and it is uncertain whether traditional transport principles apply to the ppt levels important to PFAS projects. Existing analytical methods are sufficient when combined with the many advances in site characterization techniques to move rapidly forward at selected sites to develop and test process‐based conceptual site models.
• Existing remediation technologies and research: Current technologies largely focus on separation (sorption, ion exchange, or sequestration). Due to diversity in PFAS properties, effective treatment will likely require treatment trains. Monitored natural attenuation will not likely involve destructive reactions, but be driven by processes such as matrix diffusion, sorption, dispersion, and dilution.

The consensus message from the Symposium participants is that PFAS present far more complex challenges to the environmental community than prior contaminants. This is because, in contrast to chlorinated solvents, PFAS are severely complicated by their mobility, persistence, toxicological uncertainties, and technical obstacles to remediation—all under the backdrop of stringent regulatory and policy developments that vary by state and will be further driven by USEPA. Concern was expressed about the time, expense, and complexity required to remediate PFAS sites and whether the challenges of PFAS warrant alternative approaches to site cleanups, including the notion that adaptive management and technical impracticability waivers may be warranted at sites with expansive PFAS plumes. A paradigm shift towards receptor protection rather than broad scale groundwater/aquifer remediation may be appropriate.     

Sediment quality assessment of Beasley Lake: bioaccumulation and effects of pesticides in Hyalella azteca

Beasley Lake is a Conservation Effects Assessment Program (CEAP) watershed in the intensively cultivated Mississippi Delta, USA. Lake sediment quality at three sites was evaluated in 2004 and 2008 for biological impairment and uptake (animal tissue pesticide residues) from 14 pesticides and three metabolites using Hyalella azteca (Saussure). Eleven pesticides and three metabolites were detected in sediment among the three sites in 2004 and all 17 compounds examined were detected among the three sites in 2008, with the herbicide atrazine having the greatest concentrations. Twenty-eight-day H. azteca survival and growth (mg w/w) indicated no survival effects at any site for either year, but growth impairment occurred in H. azteca exposed to sediments in 2004, whereas growth enhancement occurred in H. azteca exposed to sediments at one site in 2008. Pesticides observed in animal tissue pesticide residues occurred more frequently and in greater concentrations in 2004 compared with 2008. Thirteen pesticides were detected in animal tissue pesticide residues in 2004, with chlorpyrifos occurring in the greatest concentrations, and six pesticides were detected in 2008, with p,p′-DDT occurring in the greatest concentrations. H. azteca tissue pesticide residues of seven pesticides, two herbicides, three insecticides, one insecticide metabolite, and p,p′-DDT, were associated with growth.     

Fume emissions during gas metal arc welding

The control of exposure to welding fumes is of increasing importance in promoting a healthy, safe and productive work environment. This article describes the effects of shielding gas composition on the amount and composition of welding fumes produced during gas metal arc welding (GMAW). The amount of fumes generated during welding was measured for steady current over a range of wire-feed speeds and arc voltages using the standard procedures contained in ANSI/AWS F1.2 [American Welding Society. ANSI/AWS F1.2. Laboratory method for measuring fume generation rates and total fume emission of welding and allied processes. Miami, Florida; 1992]. Results of these measurements show that the fume formation rates (FFRs) increase with CO₂ and O₂ in the shielding gas mixture. The lowest FFRs were obtained with the mixtures of Ar?+?2%CO₂ and Ar?+?3%CO₂?+?1%O₂. The highest FFRs were obtained with the mixtures of Ar?+?18%CO₂ and Ar?+?5%CO₂?+?4%O₂. The welding fumes contains mainly iron, manganese, silicon, titanium and sodium under oxide forms. The fume cluster particles have dimensions between 0.5 and 2?µm. The FFR was found to be governed by the transfer modes of molten metal, i.e. the current intensity and arc voltage, as well as by the shielding gas mixtures composition. Thus these parameters have to be taken into consideration before designing a welding process. Whenever possible, users of GMAW should use the lowest current intensity. However, when this is not possible, due to the constraints of process productivity, welders should use higher currents, but with Ar?+?2%CO₂ and Ar?+?3%CO₂?+?1%O₂ shielding mixtures, which will lead to smaller fume emissions.     

Formation of tidal starting-jet vortices through idealized barotropic inlets with finite length

This paper presents a surface particle image velocimetry study to investigate the dynamics of shallow starting-jet dipoles formed by tidal flow through inlets and their interaction with vorticity formed at the inlet channel lateral boundaries. Vortical structure in the flow field is identified using a local swirl strength criterion evaluated from the two-dimensional flow field. The starting jet dipole vortices and vortices formed as the lateral boundary layers are expelled during flow reversal are characterized by their trajectory, size, and circulation. Using these quantities, a model is developed to predict the size and strength of the expelled lateral boundary layer vortices based on the inlet velocity, channel length, and width of the lateral boundary layer. The expelled boundary layer vortices are found to disrupt the formation of the primary tidal jet dipole through two mechanisms. First, because the boundary layer vortices themselves form a dipole with each half of the starting-jet dipole, the starting-jet vortices are pulled apart and advected away from the inlet mouth early in the tidal cycle, resulting in a reduction in the spin-up time and the amount of vorticity input during starting-jet vortex formation. Second, the advection of each dipole away from the inlet disconnects each starting-jet vortex from the starting jet; hence, the vortices are not fed by fluid in the jet or energized by shear in the jet boundary layers. These influences of the lateral boundary layer on the starting-jet vortices’ formation and propagation are found to be a function of the channel length L, maximum velocity U, and tidal period T, resulting in a predictive value to characterize their trajectory, strength, and evolution.