SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Preliminary measurements of summer nitric acid and ammonia concentrations in the Lake Tahoe Basin air-shed: implications for dry deposition of atmospheric nitrogen

Over the past 50 years, Lake Tahoe, an alpine lake located in the Sierra Nevada mountains on the border between California and Nevada, has seen a decline in water clarity. With significant urbanization within its borders and major urban areas 130 km upwind of the prevailing synoptic airflow, it is believed the Lake Tahoe Basin is receiving substantial nitrogen (N) input via atmospheric deposition during summer and fall. We present preliminary inferential flux estimates to both lake surface and forest canopy based on empirical measurements of ambient nitric acid (HNO3), ammonia (NH3), and ammonium nitrate (NH4NO3) concentrations, in an effort to identify the major contributors to and ranges of atmospheric dry N deposition to the Lake Tahoe Basin. Total flux from dry deposition ranges from 1.2 to 8.6 kg N ha-1 for the summer and fall dry season and is significantly higher than wet deposition, which ranges from 1.7 to 2.9 kg N ha-1 year-1. These preliminary results suggest that dry deposition of HNO3 is the major source of atmospheric N deposition for the Lake Tahoe Basin, and that overall N deposition is similar in magnitude to deposition reported for sites exposed to moderate N pollution in the southern California mountains.     

Biochemical composition of Nephrops norvegicus : changes associated with ovary maturation

Changes in the biochemical composition of the ovary of Nephrops norvegicus (L.) were examined throughout maturation at stations with fast and slow growing individuals in Scottish waters and in the Mediterranean. Ovary index (ovary wt:total body wt) increased significantly with maturation. Lipid, protein and water content of the ovary increased with maturation, while carbohydrate content decreased. Similar changes were also identified in the hepatopancreas. Significant spatial differences in ovary and hepatopancreas composition were identified, which may be related to whole-body growth rate. The ovary maturation scale commonly used for N. norvegicus was shown to reflect biochemically distinct stages in ovary development. Received: 7 February 1997 / Accepted: 25 February 1997     

Environmental Surveillance for Noroviruses in Selected South African Wastewaters 2015–2016: Emergence of the Novel GII.17

Norovirus (NoV) GII.4 is the predominant genotype associated with gastroenteritis pandemics and new strains emerge every 2–3 years. Between 2008 and 2011, environmental studies in South Africa (SA) reported NoVs in 63% of the sewage-polluted river water samples. The aim of this study was to assess whether wastewater samples could be used for routine surveillance of NoVs, including GII.4 variants. From April 2015 to March 2016, raw sewage and effluent water samples were collected monthly from five wastewater treatment plants in SA. A total of 108 samples were screened for NoV GI and GII using real-time RT-qPCR. Overall 72.2% (78/108) of samples tested positive for NoVs with 4.6% (5/108) GI, 31.5% (34/108) GII and 36.1% (39/108) GI + GII strains being detected. Norovirus concentrations ranged from 1.02 × 10² to 3.41 × 10⁶ genome copies/litre for GI and 5.00 × 10³ to 1.31 × 10⁶ genome copies/litre for GII. Sixteen NoV genotypes (GI.2, GI.3, GI.4, GI.5, GI.6, GII.2, GII.3, GII.4, GII.7, GII.9, GII.10, GII.14, GII.16, GII.17, GII.20, and GII.21) were identified. Norovirus GII.2 and GII.17 co-dominated and the majority of GII.17 strains clustered with the novel Kawasaki 2014 variant. Sewage surveillance facilitated detection of Kawasaki 2014 in SA, which to date has not been detected with surveillance in children with gastroenteritis <5 years of age. Combined surveillance in the clinical setting and environment appears to be a valuable strategy to monitor emergence of NoV strains in countries that lack NoV outbreak surveillance.     

Water quality requirements for sustaining aquifer storage and recovery operations in a low permeability fractured rock aquifer

A changing climate and increasing urbanisation has driven interest in the use of aquifer storage and recovery (ASR) schemes as an environmental management tool to supplement conventional water resources. This study focuses on ASR with stormwater in a low permeability fractured rock aquifer and the selection of water treatment methods to prevent well clogging. In this study two different injection and recovery phases were trialed. In the first phase ~1380 m(3) of potable water was injected and recovered over four cycles. In the second phase ~3300 m(3) of treated stormwater was injected and ~2410 m(3) were subsequently recovered over three cycles. Due to the success of the potable water injection cycles, its water quality was used to set pre-treatment targets for harvested urban stormwater of ≤ 0.6 NTU turbidity, ≤ 1.7 mg/L dissolved organic carbon and ≤ 0.2 mg/L biodegradable dissolved organic carbon. A range of potential ASR pre-treatment options were subsequently evaluated resulting in the adoption of an ultrafiltration/granular activated carbon system to remove suspended solids and nutrients which cause physical and biological clogging. ASR cycle testing with potable water and treated stormwater demonstrated that urban stormwater containing variable turbidity (mean 5.5 NTU) and organic carbon (mean 8.3 mg/L) concentrations before treatment could be injected into a low transmissivity fractured rock aquifer and recovered for irrigation supplies. A small decline in permeability of the formation in the vicinity of the injection well was apparent even with high quality water that met turbidity and DOC but could not consistently achieve the BDOC criteria.     

The measurement of water scarcity: Defining a meaningful indicator

Metrics of water scarcity and stress have evolved over the last three decades from simple threshold indicators to holistic measures characterising human environments and freshwater sustainability. Metrics commonly estimate renewable freshwater resources using mean annual river runoff, which masks hydrological variability, and quantify subjectively socio-economic conditions characterising adaptive capacity. There is a marked absence of research evaluating whether these metrics of water scarcity are meaningful. We argue that measurement of water scarcity (1) be redefined physically in terms of the freshwater storage required to address imbalances in intra- and inter-annual fluxes of freshwater supply and demand; (2) abandons subjective quantifications of human environments and (3) be used to inform participatory decision-making processes that explore a wide range of options for addressing freshwater storage requirements beyond dams that include use of renewable groundwater, soil water and trading in virtual water. Further, we outline a conceptual framework redefining water scarcity in terms of freshwater storage.     

Mechanisms of nutrient attenuation in a subsurface flow riparian wetland

Riparian wetlands are transition zones between terrestrial and aquatic environments that have the potential to serve as nutrient filters for surface and ground water due to their topographic location. We investigated a riparian wetland that had been receiving intermittent inputs of NO3- and PO4(3-) during storm runoff events to determine the mechanisms of nutrient attenuation in the wetland soils. Few studies have shown whether infrequent pulses of NO3- are sufficient to maintain substantial denitrifying communities. Denitrification rates were highest at the upstream side of the wetland where nutrient-rich runoff first enters the wetland (17-58 microg N2O-N kg soil(-1) h(-1)) and decreased further into the wetland. Carbon limitation for denitrification was minor in the wetland soils. Samples not amended with dextrose had 75% of the denitrification rate of samples with excess dextrose C. Phosphate sorption isotherms suggested that the wetland soils had a high capacity for P retention. The calculated soil PO4(3-) concentration that would yield an equilibrium aqueous P04(3-) concentration of 0.05 mg P L(-1) was found to be 100 times greater than the soil PO4(3-) concentration at the time of sampling. This indicated that the wetland could retain a large additional mass of PO4(3-) without increasing the dissolved P04(3-) concentrations above USEPA recommended levels for lentic waters. These results demonstrated that denitrification can be substantial in systems receiving pulsed NO3- inputs and that sorption could account for extensive PO4(3-) attenuation observed at this site.     

REGION,LANDSCAPE, AND SCALE EFFECTS ON LAKE SUPERIOR TRIBUTARY WATER QUALITY1

ABSTRACT: In 1998 and 1999, third‐order watersheds in high mature forest (HMF) and low mature forest (LMF) classes were selected along gradients of watershed storage within each of two hydrogeomorphic regions in the Lake Superior Basin to evaluate threshold effects of storage on hydrologic regimes and watershed exports. Differences were detected between regions (North and South Shore) for particulates, nutrients, and pH, with all but silica values higher for South Shore streams (p < 0.05). Mature forest effects were detected for turbidity, nutrients, color, and alkalinity, with higher values in the LMF watersheds, that is, watersheds with less that 50 percent mature forest cover. Dissolved N, ammonium, N:P, organic carbon, and color increased, while suspended solids, turbidity, and dissolved P decreased as a function of storage. Few two‐way interactions were detected between region and mature forest or watershed storage, thus threshold based classification schemes could be used to extrapolate effects across regions. Both regional differences in water quality and those associated with watershed attributes were more common for third‐order streams in the western Lake Superior drainage basin as compared with second‐order streams examined in an earlier study. Use of ecoregions alone as a basis for setting regional water quality criteria would have led to misinterpretation of reference condition and assessment of impacts in the Northern Lakes and Forest Ecoregion.     

Cumulative silvicultural impacts on watersheds: A hydrologic and regulatory dilemma

Because of the nature of watersheds, the hydrologic and erosional impacts of logging and related road-building activities may move offsite, affecting areas downslope and downstream from the operation. The degree to which this occurs depends on the interaction of many variables, including soils, bedrock geology, vegetation, the timing and size of storm events, logging technology, and operator performance. In parts of northwestern California, these variables combine to produce significant water quality degradation, with resulting damage to anadromous fish habitat.Examination of recent aerial photographs, combined with a review of public records, shows that many timber harvest operations were concentrated in a single 83 km² watershed in the lower Klamath River Basin within the past decade. The resulting soil disturbance in this case seems likely to result in cumulative off-site water quality degradation in the lower portion of the Basin.In California, both state and federal laws require consideration of possible cumulative effects of multiple timber harvest operations. In spite of recent reforms that have given the state a larger role in regulating forest practices on private land, each timber harvest plan is still evaluated in isolation from other plans in the same watershed. A process of collaborative state-private watershed planning with increased input of geologic information offers the best long-term approach to the problem of assessing cumulative effects of multiple timber harvest operations. Such a reform could ultimately emerge from the ongoing water quality planning process under Section 208 of the amended Federal Water Pollution Control Act.     

Development of the Spatial Rainfall Generator (SRGEN) for the Agricultural Policy/Environmental Extender Model

Accurate spatial representation of climatic patterns is often a challenge in modeling biophysical processes at the watershed scale, especially where the representation of a spatial gradient in rainfall is not sufficiently captured by the number of weather stations. The spatial rainfall generator (SRGEN) is developed as an extension of the “weather generator” (WXGEN), a component of the Agricultural Policy/Environmental eXtender (APEX) model. SRGEN generates spatially distributed daily rainfall using monthly weather statistics available at multiple locations in a watershed. The spatial rainfall generator as incorporated in APEX is tested on the Cowhouse watershed (1,178 km²) in central Texas. The watershed presented a significant spatial rainfall gradient of 2.9 mm/km in the lateral (north‐south) directions based on four rainfall gages. A comparative analysis between SRGEN and WXGEN indicates that SRGEN performs well (PBIAS = 2.40%). Good results were obtained from APEX for streamflow (NSE = 0.99, PBIAS = 8.34%) and NO₃‐N and soluble P loads (PBIAS ≈ 6.00% for each, respectively). However, APEX underpredicted sediment yield and organic N and P loads (PBIAS: 24.75‐27.90%) with SRGEN, although its uncertainty in output was lower than WXGEN results (PBIAS: ?13.02 to ?46.13%). The overall improvement achieved in rainfall generation by SRGEN is demonstrated to be effective in the improving model performance on flow and water quality output.