Comparison of micrometeorological and two-film estimates of air–water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.     

Remote sampling of a CO2 point source in an urban setting

High frequency CO₂ and wind speed measurements were used to examine the urban baseline eddy covariance CO₂ flux and analyse the CO₂ rich plume from a local power station. A reliable relationship between high frequency CO₂ maxima and the rate of CO₂ emission at the power station was established. This relationship was shown to be highly dependant on wind speed. The ensemble mean plume was found to be Gaussian in horizontal profile with a width dependant on wind speed. The relationship between peak CO₂ mixing ratio and averaging time was shown to be a simple power law with a time exponent of approximately 0.5. The large, short pulses in CO₂ mixing ratio in the power plant plume were found to have an approximately Lorentzian shape. These pulses generated negative vertical eddy flux measurements so data from the plume sector were necessarily excluded from the flux baseline results. The plume-excluded flux had a similar magnitude and variability to those reported in other urban CO₂ flux studies despite this site not being ideal due to the proximity of roughness elements to the measurement point.     

Misuse of null hypothesis significance testing: would estimation of positive and negative predictive values improve certainty of chemical risk assessment?

Although generally misunderstood, the p value is the probability of the test results or more extreme results given H₀ is true: it is not the probability of H₀ being true given the results. To obtain directly useful insight about H₀, the positive predictive value (PPV) and the negative predictive value (NPV) may be useful extensions of null hypothesis significance testing (NHST). They provide information about the probability of statistically significant and non-significant test outcomes being true based on an a priori defined biologically meaningful effect size. The present study explores the utility of PPV and NPV in an ecotoxicological context by using the frequently applied Daphnia magna reproduction test (OECD guideline 211) and the chemical stressor lindane as a model system. The results indicate that especially the NPV deviates meaningfully between a test design strictly following the guideline and an experimental procedure controlling for α and β at the level of 0.05. Consequently, PPV and NPV may be useful supplements to NHST that inform the researcher about the level of confidence warranted by both statistically significant and non-significant test results. This approach also reinforces the value of considering α, β, and a biologically meaningful effect size a priori.     

Spatial distribution of perfluoroalkyl acids in the Pearl River of Southern China

An intensive campaign was conducted in September 2012 to collect surface water samples along the tributaries of the Pearl River in southern China. Thirteen perfluoroalkyl acids (PFAAs), including perfluorocarboxylates (PFCAs, C4–C11) and perfluorosulfonates (PFSAs, C4, C6–C8, and C10), were determined using high-performance liquid chromatography/negative electrospray ionization–tandem mass spectrometry (HPLC/(-)ESI–MS/MS). The concentrations of total PFAAs (ΣPFAAs) ranged from 3.0 to 52 ng L⁻¹, with an average of 19 ± 12 ng L⁻¹. The highest concentrations of ΣPFAAs were detected in the surface water of the Dong Jiang tributary (17–52 ng L⁻¹), followed by the main stream (13–26 ng L⁻¹) and the Sha Wan stream (3.0–4.5 ng L⁻¹). Perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorooctane sulfonate (PFOS) were the three most abundant PFAAs and on average accounted for 20%, 24%, and 19% of ΣPFAAs, respectively. PFBS was the most abundant PFAA in the Dong Jiang tributary, and PFOA was the highest PFAA in the samples from the main stream of the Pearl River. A correlation was found between PFBS and PFOA, which suggests that both of these PFAAs originate from common source(s) in the region. Nevertheless, the slope of PFBS/PFOA was different in the different tributaries sampled, which indicates a spatial difference in the source profiles of the PFAAs.     

Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China

Dechlorane Plus (DP) has been determined in surface sediments from three Chinese coastal bays, e.g. Jiaozhou, Sishili and Taozi Bay in North China. DP concentrations ranged from <1.2 to 187 pg g⁻¹ dry weight (dw) (mean: 24.7 pg g⁻¹ dw) in Jiaozhou Bay, <1.2 to 135 pg g⁻¹ dw (mean 69.9 pg g⁻¹ dw) in Sishili Bay and <1.2 to 66.7 pg g⁻¹ dw (mean: 40.4 pg g⁻¹ dw) in Taozi Bay, respectively. Additionally, two dechlorinated species were quantified, which accounted for 0.6-5.1% of the ∑DP concentration.The f_syn values (syn-isomer/(syn- + anti-isomer)) in sediments from Jiaozhou Bay (mean 0.29) were close to the technical DP mixture (0.2-0.4), probably indicating local inputs of DP. In contrast, sediments in Sishili and Taozi Bay showed much lower f_syn values (mean 0.16). During transportation the DP isomers are subject to stereo selective degradation which partly resulted in the relative enrichment of anti-DP in coastal sediments.     

Chemical composition of burnt smell caused by accidental fires: environmental contaminants

The chemical composition of the odors typical of fires has recently been deciphered. Basically the constituents are mixtures of acetophenone, benzyl alcohol, hydroxylated derivatives of benzaldehyde, methoxylated and/or alkylated phenols and naphthalene. This finding makes it possible to develop objective, practical analytic measurement methods for the burnt smell as a contribution to improving fire damage assessment and remediation monitoring. With the aid of an artificially produced burnt smell and a panel of testers the odor detection threshold of a test mixture was determined olfactometrically to 2 μg m⁻³. Using a defined burnt-smell atmosphere in a test chamber, analytical methods with active sampling, the adsorbents XAD 7 and TENAX TA, and GC/MS measurement were then optimized and tested with a view to being able to carry out sensitive quantitative measurement of burnt smells. A further practical method with particular application to the qualitative characterization of this odor is based on the use of a new SPME (solid-phase microextraction) field sampler with DVB/CAR/PDMS (divinylbenzene/Carboxen™/polydimethylsiloxane) fibers.     

Quantification of nitrate leaching from German forest ecosystems by use of a process oriented biogeochemical model

Simulations with the process oriented Forest-DNDC model showed reasonable to good agreement with observations of soil water contents of different soil layers, annual amounts of seepage water and approximated rates of nitrate leaching at 79 sites across Germany. Following site evaluation, Forest-DNDC was coupled to a GIS to assess nitrate leaching from German forest ecosystems for the year 2000. At national scale leaching rates varied in a range of 0–>80 kg NO₃–N ha⁻¹ yr⁻¹ (mean 5.5 kg NO₃–N ha⁻¹ yr⁻¹). A comparison of regional simulations with the results of a nitrate inventory study for Bavaria showed that measured and simulated percentages for different nitrate leaching classes (0–5 kg N ha⁻¹ yr⁻¹:66% vs. 74%, 5–15 kg N ha⁻¹ yr⁻¹:20% vs. 20%, >15 kg N ha⁻¹ yr⁻¹:14% vs. 6%) were in good agreement. Mean nitrate concentrations in seepage water ranged between 0 and 23 mg NO₃–N l⁻¹.     

Organophosphorus flame retardants and plasticizers in the atmosphere of the North Sea

Air samples collected in the German part of the North Sea from March to July 2010 were investigated for organophosphorus compounds (OPs) being applied as flame retardants and plasticizers. The ∑₈OPs concentration ranged from 110 to 1400 pg m⁻³ while tris(2-chloroisopropyl) phosphate (TCPP) dominated all samples with individual concentrations up to 1200 pg m⁻³. The highest concentrations were observed in continental air masses showing the high influence of industrialized regions including production sites on atmospheric emissions and concentrations. The occurrence of OPs even in oceanic/Arctic air masses shows that OPs can undergo long-range atmospheric transport. Dry particle-bound deposition fluxes from 9 to 240 ng m⁻² d⁻¹ for ∑₈OPs were estimated leading to a minimum annual flux of 710 ± 580 kg y⁻¹ OPs into the German North Sea. This study presents the first occurrence of OPs in the marine atmosphere together with important information on their long-range transport potential.