A WATERSHED-LEVEL ECOLOGICAL RISK ASSESSMENT METHODOLOGY1

ABSTRACT: We present an ecological risk assessment methodology at the watershed level for freshwater ecosystems. The major component is a pollutant transport and fate model (a modified EUTROMOD) with an integrated uncertainty analysis utilizing a two-phase Monte Carlo procedure. The uncertainty analysis methodology distinguishes between knowledge uncertainty and stochastic variability. The model assesses the ecological risk of lentic (lake) ecosystems in response to the stress of excess phosphorus resulting in eutrophication. The methodology and model were tested on the Wister Lake watershed in Oklahoma with the lake and its trophic state as the endpoint for ecological risk assessment. A geographic information system was used to store, manage, and manipulate spatially referenced data for model input.     

Stream Temperature Patterns over 35 Years in a Managed Forest of Western Washington

Stream temperature changes as a result of forest practices have been a concern in the Pacific Northwest for several decades. As a result of this concern, stream protection requirements for forest lands were first adopted in the early 1970s and have become progressively more stringent. While there have been multiple studies examining the effects of stream protection buffers on water temperature, there are few studies examining temperature patterns over long periods on intensively managed forests. Water temperature in the upper Deschutes River watershed, Washington has been monitored since 1975 and represents one of the longest studies of water quality on managed forests in the Pacific Northwest. This data record, collected from basins of varying sizes, has enabled us to examine the combined effects of hydro‐climatic patterns and forest management on stream temperature. Effects of harvest conducted prior to buffer regulations were clearly identifiable and most pronounced on smaller streams. We were not able to detect any response on larger channels to more recent timber harvest where riparian buffers were required. This analysis also emphasizes that it is critical to account for changing climate when examining long‐term temperature patterns. We found that in many cases the temperature improvements associated with more stringent buffer requirements implemented over the last 35 years in the Deschutes watershed have been offset by warming climatic conditions.     

Ricin as a weapon of mass terror — Separating fact from fiction

In recent years there has been an increased concern regarding the potential use of chemical and biological weapons for mass urban terror. In particular, there are concerns that ricin could be employed as such an agent. This has been reinforced by recent high profile cases involving ricin, and its use during the cold war to assassinate a high profile communist dissident. Nevertheless, despite these events, does it deserve such a reputation? Ricin is clearly toxic, though its level of risk depends on the route of entry. By ingestion, the pathology of ricin is largely restricted to the gastrointestinal tract where it may cause mucosal injuries; with appropriate treatment, most patients will make a full recovery. As an agent of terror, it could be used to contaminate an urban water supply, with the intent of causing lethality in a large urban population. However, a substantial mass of pure ricin powder would be required. Such an exercise would be impossible to achieve covertly and would not guarantee success due to variables such as reticulation management, chlorination, mixing, bacterial degradation and ultra-violet light. By injection, ricin is lethal; however, while parenteral delivery is an ideal route for assassination, it is not realistic for an urban population. Dermal absorption of ricin has not been demonstrated. Ricin is also lethal by inhalation. Low doses can lead to progressive and diffuse pulmonary oedema with associated inflammation and necrosis of the alveolar pneumocytes. However, the risk of toxicity is dependent on the aerodynamic equivalent diameter (AED) of the ricin particles. The AED, which is an indicator of the aerodynamic behaviour of a particle, must be of sufficiently low micron size as to target the human alveoli and thereby cause major toxic effects. To target a large population would also necessitate a quantity of powder in excess of several metric tons. The technical and logistical skills required to formulate such a mass of powder to the required size is beyond the ability of terrorists who typically operate out of a kitchen in a small urban dwelling or in a small ill-equipped laboratory. Ricin as a toxin is deadly but as an agent of bioterror it is unsuitable and therefore does not deserve the press attention and subsequent public alarm that has been created.     

Fluorinated alkyl compounds including long chain carboxylic acids in wild bird livers from Japan

A wide range of fluorinated alkyl compounds (FACs) has been reported in wildlife in various locations in the world. However, such information regarding Japanese wildlife is rarely found. In the present study, we investigated the occurrence of 21 FACs, including perfluorinated alkyl sulfonates (PFASs), perfluorinated carboxylates (PFCAs), and fluorotelomer acids, in the livers of 10 wild bird species from two regions in northern Japan. To avoid interferences, FACs were quantified by a recently developed method using acetonitrile and solid-phase extraction followed by an ion exchange HPLC column separation. Apart from perfluorooctane sulfonate (PFOS), which was found at the highest levels of all the compounds detected, several long chain perfluorinated carboxylates (PFCAs) from C8 to C16, particularly perfluorotetradecanoic acid (PFTeDA) and perfluorohexadecanoic acid (PFHxDA), were detected for the first time. Additionally, 7:3 FTCA, a fluorotelomer acid, was also detected in most swan livers from Miyagi prefecture and all the birds from Tochigi prefecture. However, none of the sulfonamides and unsaturated telomer acids were detected in any species. Swans seem to be the least exposed wild birds to FACs among the investigated birds, signifying that feeding habits may reflect FAC accumulation in wild birds. The highest total concentration of detected FACs was 405 ng g⁻¹ wet wt., which was found in a Japanese sparrowhawk, indicating that the top predatory wild birds can accumulate several long chain carboxylic acids. However, the current FAC concentrations found in livers may suggest that these compounds alone would not cause a severe toxic effect in these species.     

Extraction of soil solution by drainage centrifugation—effects of centrifugal force and time of centrifugation on soil moisture recovery and solute concentration in soil moisture of loess subsoils

The solute concentration in the subsoil beneath the root zone is an important parameter for leaching assessment. Drainage centrifugation is considered a simple and straightforward method of determining soil solution chemistry. Although several studies have been carried out to determine whether this method is robust, hardly any results are available for loess subsoils. To study the effect of centrifugation conditions on soil moisture recovery and solute concentration, we sampled the subsoil (1.5–3.0 m depth) at commercial farms in the loess region of the Netherlands. The effect of time (20, 35, 60, 120 and 240 min) on recovery was studied at two levels of the relative centrifugal force (733 and 6597g). The effect of force on recovery was studied by centrifugation for 35 min at 117, 264, 733, 2932, 6597 and 14,191g. All soil moisture samples were chemically analysed. This study shows that drainage centrifugation offers a robust, reproducible and standardised way for determining solute concentrations in mobile soil moisture in silt loam subsoils. The centrifugal force, rather than centrifugation time, has a major effect on recovery. The maximum recovery for silt loams at field capacity is about 40%. Concentrations of most solutes are fairly constant with an increasing recovery, as most solutes, including nitrate, did not show a change in concentration with an increasing recovery.     

Gas chromatographic fingerprinting of crude oil from Idu-Ekpeye oil spillage site in Niger-delta, Nigeria

Samples were collected from an oil polluted site in Niger-delta, Nigeria. Gas chromatographic analyses carried out on the samples revealed an abundance of n-alkanes within the n-C₈–n-C₂₃ region. The pristane/phytane ratio of 5.70 obtained for the samples depicted a plant/terrestrial source input and a possible oxic depositional environment. The n-C₁₇/pristane and n-C₁₈/phytane ratios of 2.80 and 2.77, respectively, suggested that the spilled oil was only slightly weathered, as corroborated by the presence of peaks in the aromatic hydrocarbon fingerprints. The polycyclic aromatic hydrocarbon (PAH) fractions showed that the hydrocarbon fractions might have undergone combustion and/or that there was bush burning at the site prior to the oil spill incidence. This is supported by the abundance of high-molecular-weight PAHs which are pyrogenic in nature. High molecular weight PAHs are products of the combustion of petroleum or its products. The phenanthrene/anthracene ratio of 0.95, fluorathene/pyrene ratio of 2.23 and the ∑ (other three to six ringed PAHs)/∑ (five alkylated PAHs) ratio far greater than unity (4.10) also affirm this. On the other hand, the benzo (a) anthracene to chrysene ratio of 0.24 confirms the petrogenic origin of the spilled oil because chrysene which is highly abundant is a fossil PAH.     

Testing of the Modified Streambank Erosion and Instream Phosphorus Routines for the SWAT Model

In some watersheds, streambanks are a source of two major pollutants, phosphorus (P) and sediment. P originating from both uplands and streambanks can be transported and stored indefinitely on floodplains, streambanks, and in closed depressions near the stream. The objectives of this study were to (1) test the modified streambank erosion and instream P routines for the Soil and Water Assessment Tool (SWAT) model in the Barren Fork Creek watershed in northeast Oklahoma, (2) predict P in the watershed with and without streambank‐derived P, and (3) determine the significance of streambank erosion P relative to overland P sources. Measured streambank and channel parameters were incorporated into a flow‐calibrated SWAT model and used to estimate streambank erosion and P for the Barren Fork Creek using modified streambank erosion and instream P routines. The predicted reach‐weighted streambank erosion was 40 kg/m vs. the measured 42 kg/m. Streambank erosion contributed 47% of the total P to the Barren Fork Creek and improved P predictions compared to observed data, especially during the high‐flow events. Of the total P entering the stream system, approximately 65% was removed via the watershed outlet and 35% was stored in the floodplain and stream system. This study successfully applied the SWAT model's modified streambank erosion and instream P routines and demonstrated that streambank‐derived P can improve P modeling at the watershed scale. Editor's note: This paper is part of the featured series on SWAT Applications for Emerging Hydrologic and Water Quality Challenges. See the February 2017 issue for the introduction and background to the series.     

Perfluoroalkyl acids in blood serum samples from children in Taiwan

Severe perfluoroalkyl acid (PFAA) contamination resulting from the fast-growing semiconductor, electrochemical, and optoelectronic industries has been determined in the river water in the vicinity of the Taipei area, Taiwan, during recent years. However, little is known about body burdens of the PFAA contaminations in local residents, especially children living in the Taipei area recently. In this study, ten target PFAA analytes consisted of three perfluorosulfonates (PFSAs) and seven perfluorocarboxylates (PFCAs) in the blood serum samples, collected from 225 healthy children with an average age of 13.6 years in the Taipei area from 2009 to 2010, were analyzed via high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS). As the dominant PFAA contaminant in the blood serum samples from Taiwanese children, perfluorooctane sulfonate (PFOS) contributed 86 % of all the target PFAA analytes, while the other nine analytes contributed less than 5 % individually. PFOS showed the highest median up to 29 ng/mL, ranging from 0.03 to 148 ng/mL, which was higher than that observed in the serum samples collected from Taiwanese children between 2006 and 2008. Statistically, serum concentrations of perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), and perfluorooctanoic acid (PFOA) had significantly positive correlations with ages of children (p?<?0.05). Furthermore, serum PFBS, PFHxS, and PFOA concentrations in the male children were considerably higher than those in the female children (p?=?0.049, p?=?0.000, p?=?0.000).     

Monitoring of PCDD/Fs and dioxin-like PCBs and seasonal variations in mussels from the Mar Grande and the Mar Piccolo of Taranto (Ionian Sea,Southern Italy)

The levels and specific profiles of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in Mytilus galloprovincialis from the Mar Grande and the Mar Piccolo of Taranto were determined during the extensive monitoring plan of Local Health Authority to assess PCDD/Fs and DL-PCBs contamination in food and farm products, within 20 km from the industrial areas of Taranto, between March and December 2011. The average Total Toxicity Equivalence (TEQ) values for the sum of PCDD/F and DL-PCBs ranged from 1.61 to 5.63 pg WHO₂₀₀₅-TEQ g^?1 wet weight basis, with the highest in the first inlet of the Mar Piccolo. In particular, DL-PCBs were the dominant chemicals in all samples, followed by PCDFs and PCDDs. Congener patterns in mussels were similar, indicating a homogeneous behavior in studied areas and, probably, the same type of source. The seasonal concentrations trend showed a relevant increase of dioxin and dioxin-like PCBs TEQs during the summer months, exceeding the limits set by the European Community for food and foodstuff. Reducing PCDD/Fs and PCBs is necessary to decrease contamination levels in order to safeguard marine ecosystem and human health in the Taranto area.