Matrix diffusion effects in the cleanup of heterogeneous aquifers

Simple mathematical models are developed to account for the rather slow mass transport of nonaqueous phase liquid (NAPL) into aqueous solution in groundwater during flushing operations. The models are based on the assumption that this bottleneck in the process is associated with diffusion in the aqueous phase in the porous medium from the location of the NAPL drops/ganglia in a region of relatively low permeability out into a region of substantially higher permeability, somewhat analogous to diffusion from a block of porous rock into a nearby fracture, where the fracture system overwhelmingly dominates the overall permeability. The models include batch flushing, flushing in a laboratory column, and a one-dimensional model for flushing by means of a single recovery well.     

Patchy distributions: Optimising sample size

A method for estimating sample size which does not require an a priori definition of desired precision, or the assumption that the population is normally distributed with constant variance, has recently been proposed. This paper discusses this method and presents five modifications which make the method easier to use and reduce the probability of estimating a larger sample size than is actually required. The method is extended and used to estimate the mean abundance of patchily distributed benthic organisms. The technique can be used to guide the design of any environmental sampling programme, be it physical, chemical or biological, where comparisons between times and/or locations are required. Trade-offs between numbers of replicates and numbers of levels/sites are discussed.     

Trend evaluation of water quality parameters in the Niagara and St. Lawrence Rivers

Physical and chemical (nutrients and major ions) indicators of water quality monitored by Environment Canada between 1977 and 1987 in the Niagara River at Niagara-on-the-Lake and in the St. Lawrence River at Wolfe Island are analyzed for seasonal and annual variations. Parametric methods such as moving averages and linear regression and nonparametric methods (Spearman's rank coefficient) are used to test for the existence of trends in these data. The results indicate that specific conductivity, sodium and chloride have decreased significantly over the period of study. During the same period there is no significant trend for either discharge and nutrients.     

Derivation of Nutrient Guidelines for Streams in Victoria, Australia

Human induced increases to nutrientconcentrations in streams have led to many agenciesdeveloping strategies and criteria for nutrientreduction. National or statewide guidelines aregenerally inappropriate, due to the natural variabilityin stream ecosystems within political boundaries. Thisstudy used an extant aquatic macroinvertebrate-basedregionalisation for the state of Victoria, Australia, asthe basis for defining regions of relatively homogeneousenvironmental character. This enabled the selection ofecologically-based regional reference sites andsubsequent characterisation of the nutrient status ofthese sites. Using an extensive biological and nutrientdata base for streams across the State, we calculated50th and 75th percentile concentrations forreference sites within each region. Using thesepercentiles in conjunction with impact and recoverystudies, we defined nutrient guidelines for each region. Although the nutrient data largely supported thebiological regionalisation, patterns in the nutrient datadid require some minor modifications for the nutrientregions. Relatively unimpacted regions with referencesites in very good-to excellent-condition were assignedguidelines largely based on the 75th percentiles. The more impacted regions, where best availablereference sites were of poorer quality, were assignedguidelines based largely on the 50th percentiles. Professional judgement and known extents of impactsacross each region provided important contributions tothe decision-making process. The derived guidelineconcentrations are comparable to several cited in theliterature and are proposed for use in monitoring,assessment and restoration targets.     

Optimizing the removal of small fish passage barriers

Removing small artificial barriers that hinder upstream migrations of fish is a major problem in riparian habitat restoration. Because of budgetary limitations, it is necessary to prioritize barrier removal and repair decisions. These have usually been based on scoring and ranking procedures, which, although simple to use, can be very inefficient in terms of increasing the amount of accessible instream habitat. We develop a novel decision-making approach, based on integer programming techniques, which optimizes repair and removal decisions. Results show based on real datasets of barrier culverts located in Washington State that scoring and ranking is over 25% below the optimum on average and a full 100% below in the worst case, producing no net habitat gain whatsoever. This is compared to a dynamic programming method that was able to find optimal solutions in less than a second, even for problems with up to several hundred variables, and a heuristic method, which found solutions with less than a 1% average optimality gap in even less time.     

Assessment of the Heavy Metal Pollution Effects on the Soil Respiration in the Baix Llobregat (Catalonia, NE Spain)

A main goal of investigations is to determine could a soilrespiration be an indicator of the soil pollution. In this case a measured levelof the soil oxygen consumption depends of its pollution. It alsomeans that the pollution reduces biological processes in edaphon.Investigated soil samples were taken from polluted andnon-polluted places in the Baix Llobregat near Barcelona (Catalonia, NE Spain). Soil samples were taken from the top ofsoil (0–5 cm) without a litter. Soil analysis were done, determining percentage shares of coarsefragments, coarse sand, fine sand, coarse silt, fine silt, clay,CaCO₃, organic matter as well as water pH and conductivityCE (1:5 [mS cm^-1]). Also were determined (in mg kg^-1)quantities of heavy metals, as Fe, Al, Mn, Zn, Cr, Ni, V, Cu, Cd, Pb.The soil respiration was investigated in temperatures15 and 30 °C and with controlled humidity.The respiration in 30 °C is number of times greater thenin 15 °C both for polluted and non-polluted soils.Particularly high coefficients of correlation between the soilrespiration and soil pollution in polluted soils were obtainedfor Pb: r = 0.75 in 15 °C and r = 0.98 in30 °C; for Ba: 0.90 and 0.57; for V: 0.99 and 0.81. In non-polluted soils highest correlation coefficients are for Pb: r = 0.70 in 15 °C; Fe: 0.60 and 0.72; Al: 0.68 and0.64; Mn: 0.51 and 0.66; Ba: 0.63 and 0.61; Cr: 0.94 and0.70; Ni: 0.64 and 0.65; Cu: 0.69 and 0.48; as well as V: 0.62in 15 °C; and Cd: 0.69 in 15 °C.This way the soil respiration could be a good indicator of the soil pollution.     

Mega-Development Trends in the Amazon: Implications for Global Change

This paper describes four global-change phenomena that are having major impacts on Amazonian forests. The first is accelerating deforestation and logging. Despite recent government initiatives to slow forest loss, deforestation rates in Brazilian Amazonia have increased from 1.1 million ha yr^–1 in the early 1990s, to nearly 1.5 million ha yr^–1 from 1992–1994, and to more than 1.9 million ha yr^–1 from 1995–1998. Deforestation is also occurring rapidly in some other parts of the Amazon Basin, such as in Bolivia and Ecuador, while industrialized logging is increasing dramatically in the Guianas and central Amazonia.The second phenomenon is that patterns of forest loss and fragmentation are rapidly changing. In recent decades, large-scale deforestation has mainly occurred in the southern and eastern portions of the Amazon — in the Brazilian states of Pará, Maranho, Rondônia, Acre, and Mato Grosso, and in northern Bolivia. While rates of forest loss remain very high in these areas, the development of major new highways is providing direct conduits into the heart of the Amazon. If future trends follow past patterns, land-hungry settlers and loggers may largely bisect the forests of the Amazon Basin.The third phenomenon is that climatic variability is interacting with human land uses, creating additional impacts on forest ecosystems. The 1997/98 El Niño drought, for example, led to a major increase in forest burning, with wildfires raging out of control in the northern Amazonian state of Roraima and other locations. Logging operations, which create labyrinths of roads and tracks in forsts, are increasing fuel loads, desiccation and ignition sources in forest interiors. Forest fragmentation also increases fire susceptibility by creating dry, fire-prone forest edges.Finally, recent evidence suggests that intact Amazonian forests are a globally significant carbon sink, quite possibly caused by higher forest growth rates in response to increasing atmospheric CO₂ fertilization. Evidence for a carbon sink comes from long-term forest mensuration plots, from whole-forest studies of carbon flux and from investigations of atmospheric CO₂ and oxygen isotopes. Unfortunately, intact Amazonian forests are rapidly diminishing. Hence, not only is the destruction of these forests a major source of greenhouse gases, but it is reducing their intrinsic capacity to help buffer the rapid anthropogenic rise in CO₂.     

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).     

Insecticide Contamination of Jamaican Environment. V. Island-Wide Rapid Survey of Residues in Surface and Ground Water

Residues of organochlorines and organophosphates were determined by gas chromatography in water and sediment from 26 locations in 17 major rivers, 7 natural springs and 13 wells across Jamaica. Samples were collected on only one occasion between May and July, 1994. Residues of endosulfan were detected in all but three rivers; -endosulfan in 15 samples of sediment (0.9–108.1, mean = 28.93, S.E. = 7.198 g kg-1) and 13 of water (0.01–0.35, mean = 0.11, S.E. = 0.035 g L-1), -endosulfan in 5 sediment (15.29–49.35, mean = 30.56, S.E. = 7.132 g kg-1) and 12 water (0.05–0.31, mean = 0.14, S.E. = 0.031 g L-1) samples, and endosulfan sulphate in waters of three rivers (0.003–0.244 g L-1). Chlorpyrifos was present in 9 sediment (0.423-135.2, mean = 18.38, S.E. = 10.699 g kg-1) and two water (0.001–0.022 g L-1) samples, diazinon and ethoprophos in the sediment of one river each. Mean levels (g L-1) of and isomers and sulphate of endosulfan were 0.16 (S.E. = 0.057), 0.12 (S.E. = 0.036) and 0.15 (S.E. = 0.089), respectively, in four of the seven springs and 0.23 (S.E. = 0.052), 0.11 (S.E. = 0.029) and 0.26 (S.E. = 0.088), respectively, in seven of the thirteen wells monitored.     

Sampling Benthic Macroinvertebrates in a Large Flood-Plain River: Considerations of Study Design, Sample Size, and Cost

Estimation of benthic macroinvertebrate populations over large spatial scales is difficult due to the high variability in abundance and the cost of sample processing and taxonomic analysis. To determine a cost-effective, statistically powerful sample design, we conducted an exploratory study of the spatial variation of benthic macroinvertebrates in a 37 km reach of the Upper Mississippi River. We sampled benthos at 36 sites within each of two strata, contiguous backwater and channel border. Three standard ponar (525 cm²) grab samples were obtained at each site ('Original Design'). Analysis of variance and sampling cost of strata-wide estimates for abundance of Oligochaeta, Chironomidae, and total invertebrates showed that only one ponar sample per site ('Reduced Design') yielded essentially the same abundance estimates as the Original Design, while reducing the overall cost by 63%. A posteriori statistical power analysis ( = 0.05, = 0.20) on the Reduced Design estimated that at least 18 sites per stratum were needed to detect differences in mean abundance between contiguous backwater and channel border areas for Oligochaeta, Chironomidae, and total invertebrates. Statistical power was nearly identical for the three taxonomic groups. The abundances of several taxa of concern (e.g., Hexagenia mayflies and Musculium fingernail clams) were too spatially variable to estimate power with our method. Resampling simulations indicated that to achieve adequate sampling precision for Oligochaeta, at least 36 sample sites per stratum would be required, whereas a sampling precision of 0.2 would not be attained with any sample size for Hexagenia in channel border areas, or Chironomidae and Musculium in both strata given the variance structure of the original samples. Community-wide diversity indices (Brillouin and 1-Simpsons) increased as sample area per site increased. The backwater area had higher diversity than the channel border area. The number of sampling sites required to sample benthic macroinvertebrates during our sampling period depended on the study objective and ranged from 18 to more than 40 sites per stratum. No single sampling regime would efficiently and adequately sample all components of the macroinvertebrate community.