Water quality trends in New Zealand rivers: 1989–2009

Recent assessments of water quality in New Zealand have indicated declining trends, particularly in the 40 % of the country’s area under pasture. The most comprehensive long-term and consistent water quality dataset is the National Rivers Water Quality Network (NRWQN). Since 1989, monthly samples have been collected at 77 NRWQN sites on 35 major river systems that, together, drain about 50 % of New Zealand’s land area. Trend analysis of the NRWQN data shows increasing nutrient concentrations, particularly nitrogen (total nitrogen and nitrate), over 21 years (1989–2009). Total nitrogen and nitrate concentrations were increasing significantly over the first 11 years (1989–2000), but for the more recent 10-year period, only nitrate concentrations continued to increase sharply. Also, the increasing phosphorus trends over the first 11 years (1989–2000) levelled off over the later 10-year period (2000–2009). Conductivity has also increased over the 21 years (1989–2009). Visual clarity has increased over the full time period which may be the positive result of soil conservation measures and riparian fencing. NRWQN data shows that concentrations of nutrients increase, and visual clarity decreases (i.e. water quality declines), with increasing proportions of pastoral land in catchments. As such, the increasing nutrient trends may reflect increasing intensification of pastoral agriculture.     

Fit-for-purpose phosphorus management: do riparian buffers qualify in catchments with sandy soils?

Hillslope runoff and leaching studies, catchment-scale water quality measurements and P retention and release characteristics of stream bank and catchment soils were used to better understand reasons behind the reported ineffectiveness of riparian buffers for phosphorus (P) management in catchments with sandy soils from south-west Western Australia (WA). Catchment-scale water quality measurements of 60 % particulate P (PP) suggest that riparian buffers should improve water quality; however, runoff and leaching studies show 20 times more water and 2 to 3 orders of magnitude more P are transported through leaching than runoff processes. The ratio of filterable reactive P (FRP) to total P (TP) in surface runoff from the plots was 60 %, and when combined with leachate, 96 to 99 % of P lost from hillslopes was FRP, in contrast with 40 % measured as FRP at the large catchment scale. Measurements of the P retention and release characteristics of catchment soils (<2 mm) compared with stream bank soil (<2 mm) and the <75-μm fraction of stream bank soils suggest that catchment soils contain more P, are more P saturated and are significantly more likely to deliver FRP and TP in excess of water quality targets than stream bank soils. Stream bank soils are much more likely to retain P than contribute P to streams, and the in-stream mixing of FRP from the landscape with particulates from stream banks or stream beds is a potential mechanism to explain the change in P form from hillslopes (96 to 99 % FRP) to large catchments (40 % FRP). When considered in the context of previous work reporting that riparian buffers were ineffective for P management in this environment, these studies reinforce the notion that (1) riparian buffers are unlikely to provide fit-for-purpose P management in catchments with sandy soils, (2) most P delivered to streams in sandy soil catchments is FRP and travels via subsurface and leaching pathways and (3) large catchment-scale water quality measurements are not good indicators of hillslope P mobilisation and transport processes.     

Regional status assessment of stony corals in the US Virgin Islands

States may protect coral reefs using biological water quality standards outlined by the Clean Water Act. This requires biological assessments with indicators sensitive to human disturbance and regional, probability-based survey designs. Stony coral condition was characterized on a regional scale for the first time in the nearshore waters of the US Virgin Islands (USVI). Coral composition, abundance, size, and health were assessed at 66 stations in the St. Croix region in fall 2007 and at 63 stations in the St. Thomas and St. John region in winter 2009. Indicators were chosen for their sensitivity to human disturbance. Both surveys were probability-based (random) designs with station locations preselected from areas covered by hardbottom and coral reef substrate. Taxa richness was as high as 21 species but more than half the area of both regions exhibited taxa richness of <10 species in the 25 m² transect area. Coral density was as high as 5 colonies m^?2 but more than half the area of both regions had <2 colonies m^?2. Both regions showed similar dominant species based on frequency of occurrence and relative abundance. Because of large colony sizes, Montastrea annularis provided more total surface area and live surface area than more abundant species. The surveys establish baseline regional conditions and provide a foundation for long-term regional monitoring envisioned by the USVI Department of Planning and Natural Resources. The probabilistic sampling design assures the data can be used in Clean Water Act reporting.     

Estimating the aquatic emissions and fate of perfluorooctane sulfonate (PFOS) into the river Rhine

The sources, distribution, levels and sinks of perfluorooctane sulfonate (PFOS) estimated to be released from areas of high population density, have been explored using the river Rhine as a case study. A comparison between modelled and measured data is presented, along with analysis of the importance of PFOS sorption in riverine systems. PFOS releases into the Rhine were estimated to be 325-690 kg/yr based on per capita emission rates of 27-57 μg day(-1) from a population of 33 million living within a 50 km zone either side of the river. Sorption of PFOS to suspended particles and sediments may alter its fate in the aquatic environment. Therefore available measured and modelled partitioning data was assessed, and K(d) values (sorption coefficient) of 7.5 and 20 were selected. This resulted in sediment-water ratios of 23-76 : 1, which are similar to ratios reported in the literature, and resulted in modelled estimates that <20% of the total PFOS entering the Rhine binds to sediments or suspended particles. The calculated discharge from the Rhine to the North Sea based on measured data was 420-2200 kg/yr; our model predictions are in good agreement with these estimates. Emission trends were accurately predicted, suggesting population density can be effectively used as a surrogate for diffuse PFOS emissions from product use, while predicted concentrations were a factor of 2-4 below measured data showing the importance of other sources. Transfer of PFOS to sediment is estimated to be minimal, and consequently discharges to the North Sea are roughly equal to PFOS releases to river water.     

A survey on the utility of the USEPA CADDIS stressor identification procedure

The Environmental Protection Agency (EPA) has made available on the worldwide web a systematic stream stressor identification procedure, the “Causal Analysis/Diagnosis Decision Information System” or CADDIS. We report here the results of a survey of regulators and scientists in 11 states who use CADDIS or another stressor identification procedure in their work. The 13 survey questions address guidelines as to what impairment scenarios to approach with stressor identification, what information is needed to perform stressor identification, and what the stakeholder role is in performing stressor identification. At the time of this survey (the summer of 2009), the EPA CADDIS website was less commonly used among the state regulators surveyed than the published EPA stressor identification document on which it is based. The respondents generally find the EPA stressor identification procedure useful and capable of being adapted to their individual needs. Survey respondents all use stressor identification in their Total Maximum Daily Load work, but also in a wide variety of other applications. All the “types of evidence” included in the CADDIS stressor identification procedure are used by the practitioners surveyed with the exception of the results of ecological simulation models. While the CADDIS documentation encourages the involvement of stakeholders in stressor identification, most respondents do not assemble stakeholder teams of local officials and citizens to participate in stressor analyses.     

Atmospheric influences on water quality: a simulation of nutrient loading for the Pearl River Basin, USA

Knowledge of water quality conditions is essential in assessing the health of riverine ecosystems. The goal of this study is to determine the degree to which water quality variables are related to precipitation and air temperature conditions for a segment of the Pearl River Basin near Bogalusa, LA, USA. The AQUATOX ecological fate simulation model is used to estimate daily total nitrogen, total phosphorus, and dissolved oxygen concentrations over a 2-year period. Daily modeled output for each variable was calibrated against reliably measured data to assess the accuracy. Observed data were plotted against simulated data for controlled and perturbed models for validation, and stepwise multiple regression analysis was used to quantify the relationships between the water quality and meteorological variables. Results suggest that daily dissolved oxygen is significantly negatively correlated to concurrent daily mean air temperature with a total explained variance of 0.679 (p?<?0.01), and monthly dissolved oxygen is significantly negatively correlated to monthly mean air temperature with a total explained variance of 0.567 (p?<?0.01). Total mean monthly phosphorus concentration is significantly positively related to the previous month's precipitation with a total explained variance of 0.302 (p?<?0.01). These relationships suggest that atmospheric conditions have a strong influence on water quality in the Pearl Basin. Therefore, environmental planners should expect that future climatic changes are likely to alter water quality.     

Numerical Modeling of a Potential Geological CO 2 Sequestration Site at Minden (Germany)

We study opportunities for CO₂ sequestration in geological formations of the state North Rhine Westphalia in Germany. Simulations are performed for evaluating a potential site within the Bunter sandstone formation near the town of Minden in a depth?of around 3,000 m using the numerical simulator TOUGHREACT. Our focus is on three CO₂ storage mechanisms: (1) hydrodynamic trapping, (2) dissolution trapping, and (3) mineral trapping. The results show that due to buoyancy the injected CO₂ phase initially migrates towards the top of the reservoir and is hydrodynamically trapped beneath the confining layer of the cap rock. Then, the CO₂ spreads laterally and dissolves partially in the formation water. The dissolution of CO₂ results in an increase of the density of the brine causing a downward migration until it settles after 10,000 years at the bottom of the reservoir. The simulations indicate that after 10,000 years, 15% (17 Mt) from a total of 114 Mt injected CO₂ are trapped hydrodynamically, 20% (23 Mt) are trapped by dissolution, and 65% (74 Mt) are fixed in newly formed carbonates such as dawsonite, ankerite, and siderite. Within our study pressure increases near the injection well by a factor of 1.1 which is lower than the upper limit usually accepted in gas storage operations. The mineral reactions cause a net decrease of porosity and in turn a decrease of permeability down to 9% of the initial value in parts of the reservoir.     

Biopolymer (Chitin) from Various Marine Seashell Wastes: Isolation and Characterization

Chitin has been produced from different sea waste sources including, molluscs (mussel and oyster shell), crustacean (prawn and crab) and fish scale (pang and silver scales) using deproteinization and demineralization as chemical methods. The conditions of chemical extraction process determine the quality of chitin. The obtained results revealed that, about 1 and 10% HCl and NaOH were adequate concentrations for deproteinization and demineralization process respectively. Chitin from oyster and crab shell waste had the highest yield of 69.65 and 60.00% while prawn, mussel shell, pang and silver scales had the lowest yield of 40.89, 35.03, 35.07 and 31.11% respectively. Chitin solubility is controlled by the quantity of protonated acetyl groups within the polymeric chain of the chitin backbone, thus on the percentage of acetylated and non-acetylated d-glucos-acetamide unit. Good solubility results were obtained in mussel, oyster and crab shells respectively. The chitin molecular weight characteristics and activity are controlled by the degree of acetylation (DA) and the distribution of acetyl group extending in the polymer chain. DA is determined by acid-base titration methods and molecular weight determined by Brookfield viscometry. Both methods are found to be effective.     

Photo-Stabilisation and UV Blocking Efficacy of Coated Macro and Nano-Rutile Titanium Dioxide Particles in Paints and Coatings

Surface treated macro and nanoparticle TiO₂ samples have been prepared, characterised and their efficiency as UV blockers evaluated in clear coatings and paints. The particle size of the ‘base’ TiO₂ has been optimised to block UV radiation and the surface treatment developed to deactivate the photocatalytic activity of the surface of the TiO₂ particles. The resultant UV blockers have been evaluated in both solvent and water-based clear coatings. Nanoparticle TiO₂ has been prepared from ‘seed’ and the particle size was controlled by calcination. It was found that the choice of particle size is a compromise between UVA absorption, UVB absorption, visible transmission and photoactivity. It has been demonstrated that TiO₂ with a crystallite size of 25 nm yields a product with the optimum properties. A range of dispersants was successfully used to disperse and mill the TiO₂. Both organic and inorganic dispersants were used; 2-amino-2-methyl-1-propanol and 1-amino-2-propanol (MIPA) and P₂O₅ and Na₂SiO₃ respectively. The surface of the nano-TiO₂ was coated with mixed oxides of silicon, aluminium, zirconium and phosphorous. Addition of the resultant coated nano-rutiles to an Isocyanate Acrylic clear coating prolonged the lifetime of that coating compared to the blank. Generally, a surface treatment based on SiO₂, Al₂O₃ and P₂O₅ was more successful than one based on ZrO₂, Al₂O₃ and P₂O₅. Higher addition levels of the surface treatment were beneficial for protecting the polymeric coating. The UV blocker products were also evaluated in a water-based acrylic, first a water-based dispersion of the UV blocker was prepared before addition to the acrylic. The dispersions and resultant acrylic thin films were evaluated using UV/Vis spectroscopy and durability assessed. The ratio of absorbance at 300:500 nm for the water-based dispersion was shown to be a good predictor of both the transparency of the resultant acrylic thin film and the durability of that film, in terms of weight loss. Macro grade titanium dioxide pigments were also prepared and coated with treatments of silica, alumina and siloxane and their photo-stabilising activity in alkyd paint film assessed and found to be directly related to the electron–hole pair mobility and trapping as determined by micro-wave spectroscopy.     

Field effectiveness evaluation of advanced driver assistance systems

Abstract

Objective: Advanced driver assistance systems (ADAS) are a class of vehicle technologies designed to increase safety by providing drivers with timely warnings and autonomously intervening to avoid hazardous situations. Though laboratory testing suggests that ADAS technologies will greatly impact crash involvement rates, real-world evidence that characterizes their effectiveness is still limited. This study evaluates and quantifies the association of ADAS technologies with the likelihood of a moderate or severe crash for new-model BMWs in the United States.

Methods: Vehicle ADAS option information for the cohort of model year 2014 and later BMW passenger vehicles sold after January 1, 2014 (n?=?1,063,503), was coded using VIN-identified options data. ADAS technologies of interest include frontal collision warning with autonomous emergency braking, lane departure warning, and blind spot detection. BMW Automated Crash Notification system data (from January 2014 to November 2017) were merged with vehicle data by VIN to identify crashed vehicles (n?=?15,507), including date, crash severity (delta V), and area of impact. Using Cox proportional hazards regression modeling, the study calculates the adjusted hazard ratio for crashing among BMW passenger vehicles with versus without ADAS technologies. The adjusted percentage reduction in moderate and severe crashes associated with ADAS is interpreted as one minus the hazard ratio.

Results: Vehicles equipped with both autonomous emergency braking and lane departure warning were 23% less likely to crash than those not equipped (hazard ratio [HR]?=?0.77; 95% confidence interval [CI], 0.73–0.81), controlling for model year, vehicle size and body type. Autonomous emergency braking and lane departure warning generally occur together, making it difficult to tease apart their individual effects. Blind spot detection was associated with a 14% reduction in crashes after controlling for the presence of autonomous emergency braking and lane departure warning (HR =0.86; 95% CI, 0.744–0.99). Differences were observed by vehicle type and crash type. The combined effect of autonomous emergency braking and lane departure warning was greater in newer model vehicles: Equipped vehicles were 13% less likely to crash (HR =0.87; 95% CI, 0.79–0.95) among 2014 model year vehicles versus 34% less likely to crash (HR =0.66; 95% CI, 0.57–0.77) among 2017 model year vehicles.

Conclusion: This robust cohort study contributes to the growing evidence on the effectiveness of ADAS technologies.