Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

Chemical properties of dissolved organic matter derived from sugarcane rind and the impacts on copper adsorption onto red soil

Dissolved organic matter (DOM), as the most active organic carbon in the soil, has a coherent affinity with heavy metals from inherent and exogenous sources. Although the important roles of DOM in the adsorption of heavy metals in soil have previously been demonstrated, the heterogeneity and variability of the chemical constitution of DOM impede the investigation of its effects on heavy metal adsorption onto soil under natural conditions. Fresh DOM (FDOM) and degraded DOM (DDOM) from sugarcane rind were prepared, and their chemical properties were measured by Fourier-transform infrared spectrometry (FTIR), excitation-emission matrix (EEM) fluorescence spectroscopes, nuclear magnetic resonance (NMR), and molecular weight distribution (MWD). They were also used in batch experiments to evaluate their effects on the adsorption of Cu(II) onto farmland red soil. Based on our results, the chemical structure and composition of DDOM greatly varied; compared with FDOM, the C/O ratio (from 24.0 to 9.6%) and fluorescence index (FI) (from 1.4 to 1.0) decreased, and high molecular weight (>10 kDa) compounds increased from 23.18 to 70.51%, while low molecular weight (<3 kDa) compounds decreased from 56.13 to 12.13%; aromaticity and humification degree were markedly enhanced. The discrepancy of FDOM and DDOM in terms of chemical properties greatly influenced Cu(II) adsorption onto red soil by affecting DOM-Cu(II) complex capacity. The FDOM inhibited the adsorption of Cu(II), while DDOM promoted adsorption, which was significantly influenced by soil pH. Maximum adsorption capacity (Q _m) was 0.92 and 5.76 mg g^?1 in the presence of FDOM and DDOM, respectively. The adsorption process with DDOM could be better described by the Langmuir model, while that with FDOM was better described by the Freundlich model. The impacts caused by the dynamic changes of the chemical properties of DOM under natural conditions should therefore be considered in the risk assessment and remediation of soils contaminated with heavy metals.     

Evaluating spectroscopic and chromatographic techniques to resolve dissolved organic matter via end member mixing analysis

Real-time or near real-time in-situ monitoring of dissolved organic matter (DOM) composition in natural waters and engineered treatment systems provides critical information to water quality scientists and engineers, particularly when the monitoring techniques can provide some information about the chemical nature of DOM. The efficacy of various indices derived from rapid, low-cost spectroscopic and chromatographic techniques to discriminate DOM composition was tested for samples prepared from well-defined mixtures of purified Aldrich humic acid (PAHA) and Suwannee River fulvic acid (SRFA). Sensitivities of the discrimination indices were examined by comparing (1) the differences between measured values and those predicted based from mass balance and the end member characteristics, and (2) the linear correlations between index values and mass ratios of the DOM mixtures. Size exclusion chromatography (SEC) results revealed that the weight-average molecular weight (MW(w)) may be a useful approach for tracking DOM mixing processes, although the number-average molecular weight (MW(n)) may be better for distinguishing different DOM compositions. Specific ultraviolet absorbance measured at 254 nm (SUVA(254)) performed better as a discrimination index than did two previously recommended absorbance ratios, both in terms of making better predictions of intermediate compositions and in exhibiting a more linear correlation with PAHA mass ratio. Several well-defined peaks in the derivative absorption spectra (301 and 314 nm for the first derivative, 217 nm for the third derivative, and 211 and 224 nm for the fourth derivative) also were found to be promising potential DOM discrimination indices. Finally, a fluorescence ratio based on humic- versus fulvic-like fluorescence proved to be a superior DOM discrimination index for the two DOM end members studied here. In general, this study illustrates the evaluation process that should be followed to develop rapid, low-cost discrimination indices to monitor DOM compositions based on end member mixing analyses.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure,biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, ¹³C and 1H Nuclear Magnetic Resonance Spectrometry (¹³C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) ¹³C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

Responses of kinetics and capacity of phenanthrene sorption on sediments to soil organic matter releasing

Soil organic matter (SOM) releasing with dissolved organic matter (DOM) formed in solution was confirmed in a sediment/water system, and the effects of SOM releasing on the sorption of phenanthrene on sediments were investigated. Inorganic salt (0–0.1 mol L^?1 NaCl) was used to adjust SOM releasing, and two sediments were prepared, the raw sediment (S1) from Weihe River, Shann’xi, China, and the eluted sediments with and without DOM supernatant remained, termed as S2a and S2b, respectively. The FTIR and ¹H NMR analysis indicate that the low molecular weight hydrophilic SOM fraction released prior to the high molecular weight hydrophobic fraction. As a response, phenanthrene sorption kinetics on S1 showed atypical and expressed as three stages: rapid sorption, pseudo sorption with partial desorption, and slow sorption, thus a defined “sorption valley” occurred in kinetic curve. In all cases, partition dominates the sorption, and sorption capacity (K_d) ranked as S2b > S1 > S2a. Compared with the alterations of sediment characters, DOM solubilization produced by SOM releasing exhibited a greater inhibitory effect on sorption with a relative contribution of 0.67. Distribution coefficients (K_doc) of PHE into DOM clusters were 2.10?×?10⁴–4.18?×?10⁴ L kg^?1, however a threshold concentration of 6.83 mg L^?1 existed in DOM solubilization. The study results will help to clarify PAHs transport and their biological fate in a sediment/water system.     

Dissipation of DDT in natural water under field conditions

Abstract

¹⁴C‐DDT dissipated gradually from natural water under outdoor conditions and declined to 40% of the applied radioactivity after 5 months. The losses are due to adsorption to particulates and volatilization from the water surface. In natural water DDT undergoes gradual conversion to DDE as the major degradation product and to a lesser extent to DDD. It may be concluded that DDT dissipates and degrades fairly rapidly in subtropical natural waters. Adsorption to particulate matter contributes to partial “removal” of DDT.     

Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.     

Preliminary characterization and source assessment of PAHs in tributary sediments of the Athabasca River,Canada

The Athabasca Oil Sands are one of four natural oil sands deposits in Northern Alberta, Canada. As a number of new mines are planned in the area, there is a need to establish background levels of natural hydrocarbon release prior to these developments. To this end, various environmental samples were taken from selected tributaries in the oil sands region of the Athabasca River Basin and analysed by gas chromatography/mass spectrometry (GC/MS) for polycyclic aromatic hydrocarbons (PAHs) and their alkylated analogues. Samples were collected over 3 years (1998–2000) to provide an increased understanding of the spatial distribution, nature and extent of natural hydrocarbon release to the environment. Results indicated that levels of total PAHs were elevated in the tributaries (up to 34·7 μg/g) compared to the main stem Athabasca River (<2 μg/g). As expected, samples from the oil sands deposits contained the greatest amounts of PAHs and alkylated PAHs. Profiles of the alkylated PAH distributions were very similar, indicating that all the samples tested were from a common petrogenic source.     

Magnetic ion exchange treatment of stabilized landfill leachate

Stabilized landfill leachate is characterized by a high concentration of non-biodegradable organic matter, which is similar in chemistry to dissolved organic matter (DOM) in the natural aquatic environment. Magnetic ion exchange (MIEX) resin treatment is well-studied in drinking water for removal of DOM from natural waters. There are fewer studies evaluating MIEX treatment of waste waters, and there is no previous work evaluating MIEX treatment of landfill leachate. This work systematically evaluated MIEX treatment of stabilized landfill leachate and evaluated the results in the context of previous studies of MIEX treatment of natural and waste waters. Five leachates from four landfills were evaluated as a function of MIEX resin dose, mixing time, and regeneration efficiency. MIEX resin removed DOM from landfill leachate, even in the presence of a reported high background concentration of inorganic ions. MIEX resin that was exhausted with leachate DOM was effectively regenerated with a concentrated NaCl solution, and regenerated MIEX resin performed similarly to virgin resin. For a majority of the leachates, the removal trend for MIEX resin was color > UV-absorbing substances > dissolved organic carbon ≈ COD > total nitrogen. Finally, MIEX resin removed a wider range of DOM from leachate than coagulation. The most important contribution of this work is that MIEX treatment of leachate followed very similar trends as MIEX treatment of natural waters, which will allow previous MIEX data to be used to estimate the treatment efficiency of other waste waters.     

Reverse osmosis sampling does not affect the protective effect of dissolved organic matter on copper and zinc toxicity to freshwater organisms

Dissolved organic matter (DOM) plays a significant role in protecting freshwater organisms against metal toxicity. To study this, reverse osmosis (RO) has been widely used as a highly efficient method for rapid collection of large quantities of DOM from natural surface waters. The objective of this study was to examine the potential impact of the RO isolation technique on the protective effects of DOM on the toxicity of copper and zinc to the cladoceran Daphnia magna and the green alga Pseudokirchneriella subcapitata. DOM was concentrated from a natural surface water using RO and at the same time a natural (unconcentrated) surface water was taken. The concentrated DOM was rediluted to the level of the natural water to obtain the so-called reconstituted water. Chemical analyses and toxicity tests were performed with both the natural surface water and the reconstituted water. First, most chemical parameters were not significantly changed by the RO sampling. For both copper and zinc, no significant differences were observed in 48 h-EC50s for D. magna and in 72 h-EC50s for P. subcapitata between the reconstituted water and the natural water. Hence, it may be concluded that reverse osmosis does not significantly affect the protective effect of natural DOM against copper and zinc toxicity.     

Seasonal changes in the chemical composition and reactivity of dissolved organic matter at the land-ocean interface of a subtropical river

Dissolved organic matter (DOM) is a critical component in aquatic ecosystems, yet its seasonal variability and reactivity remain not well constrained. These were investigated at the land-ocean interface of a subtropical river (Minjiang River, SE China), using absorption and fluorescence spectroscopy. The annual export flux of dissolved organic carbon (DOC) from the Minjiang River (5.48 × 10¹⁰ g year^?1) was highest among the rivers adjacent to the Taiwan Strait, with 72% occurring in spring and summer. The freshwater absorption coefficient a₂₈₀, DOC-specific UV absorbance SUVA₂₅₄ and humification index HIX were higher, while the spectral slope S_275–295 and biological index BIX were lower in summer than in winter. This suggests intensified export of terrestrial aromatic and high molecular weight constituents in the rainy summer season. Six fluorescent components were identified from 428 samples, including humic-like C1–C3, tryptophan-like C4 and C6, and tyrosine-like C5. The freshwater levels of four components (C1, C2, C4, and C6) were lower while that of C5 was higher in the wet season than in the dry season, suggesting contrasting seasonal variations of different constituents. Laboratory experiments were performed to assess the effects of photochemical and microbial degradation on DOM. Photo-degradation removed chromophoric and fluorescent DOM (CDOM and FDOM) effectively, which was stronger (i) for high molecular weight/humic constituents and (ii) during summer under higher solar radiation. Microbial degradation under laboratory controlled conditions generally showed little effect on DOC, and had smaller impact on CDOM and FDOM in winter than in summer. Overall, this study showed notable seasonal changes in the chemical composition and reactivity of DOM at the land-ocean interface, and demonstrated the significant effects of photo-degradation.

     

Investigation on the Chemical Structure of Nonextractable Residues of the Fungicide Cyprodinil in Spring Wheat Using 13C-C1-Phenyl-Cyprodinil on 13C-Depleted Plants—An Alternative Approach to Investigate Nonextractable Residues

Abstract

¹³C-labelled cyprodinil was applied on ¹³C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of ¹⁴C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The ¹³C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.     

Preliminary characterization and source assessment of PAHs in tributary sediments of the Athabasca River,Canada

The Athabasca Oil Sands are one of four natural oil sands deposits in Northern Alberta, Canada. As a number of new mines are planned in the area, there is a need to establish background levels of natural hydrocarbon release prior to these developments. To this end, various environmental samples were taken from selected tributaries in the oil sands region of the Athabasca River Basin and analysed by gas chromatography/mass spectrometry (GC/MS) for polycyclic aromatic hydrocarbons (PAHs) and their alkylated analogues. Samples were collected over 3 years (1998-2000) to provide an increased understanding of the spatial distribution, nature and extent of natural hydrocarbon release to the environment. Results indicated that levels of total PAHs were elevated in the tributaries (up to 34.7 µg/g) compared to the main stem Athabasca River (<2 µg/g). As expected, samples from the oil sands deposits contained the greatest amounts of PAHs and alkylated PAHs. Profiles of the alkylated PAM distributions were very similar, indicating that all the samples tested were from a common petrogenic source.     

Study on the spectral and Cu (II) binding characteristics of DOM leached from soils and lake sediments in the Hetao region

Introduction

Dissolved organic matter (DOM) is the most active component in environmental system and its chemical and structural characteristics most likely influence its biodegradation. Four surface soil (0?C20?cm) and three core sediment samples (0?C10?cm) were collected from Wuliangsuhai Lake. The objectives of this study were to investigate the spectral properties and humification degree of DOM and to determine and discuss comparatively the complexing capacities and stability constants of DOM by Cu (II) in the Hetao region.

Materials and methods

In this study, fluorescence spectra and fluorescence quenching methods were used to evaluate the humification degree of DOM and calculate the complexing capacities and the stability constants between DOM and Cu (II).

Results and discussion

Two defined peaks, at wavelengths of 260??300?nm (peak I) and 300??350?nm (peak II), could be identified for soil DOM at a ???? value of 30?nm. In sediment DOM extracts, a third peak (III) was observed near 364?nm. The results show that there is a significant difference in the structure of DOM because of different sources. The humification degree is significantly higher for soil samples than those of sediment samples. The FT-IR spectra of DOM show that structure in sediment DOM is more functional groups than those in soil DOM. DOM has a stronger Cu binding affinity in soils than in sediment in the Hetao region, which may lead to potentially significant influence on the migration and transformation of Cu (II).     

Distinguishing sources of groundwater nitrate by 1H NMR of dissolved organic matter

Dissolved organic matter (DOM) originating from a certain source usually carries characteristic marks in its molecular structures that can be recognized by spectroscopic analysis. Sources of water-borne contaminants, such as nitrate, can be identified by recognition of the characteristics of DOM entrained in the water. In this study, DOM in groundwaters sampled from a dairy/crop production area (Chino Basin, CA) was analyzed by 1H nuclear magnetic resonance (1H NMR). Results showed that DOM derived from natural soil organic matter has a characteristic resonance at a chemical shift region of 4.0-4.3 ppm, while DOM derived from dairy wastes has a characteristic resonance at a lower chemical shift region of 3.2-3.6 ppm. These signature resonances were then used to distinguish the origins of nitrate in the groundwater. It was found that disposal of dairy wastes on croplands is the primary source of nitrate contamination in groundwater underlying the Chino Basin dairy area.     

Quantitative and qualitative characteristics of dissolved organic matter from eight dominant aquatic macrophytes in Lake Dianchi, China

The aim of this research was to determine and compare the quantitative and qualitative characteristics of dissolved organic matters (DOM) from eight aquatic macrophytes in a eutrophic lake. C, H, N, and P in ground dry leaves and C, N, and P in DOM of the species were determined, and C/N, C/P, C/H, DOC/C, TDN/N, TDP/P, DOC/TDN, and DOC/TDP were calculated. Chemical structures of the DOM were characterized by the use of multiple techniques including UV-visible, FT-IR, and ¹³C CP/MAS spectra. The results showed subtle differences in quantity and quality of DOM among species and life-forms. Except oriental pepper which had a C/H of 0.7, C/H of all the other species was 0.6. C/N and C/P of ground leaves was 10.5–17.3 and 79.4–225.3, respectively, which were greater in floating and submerged species than in the others. Parrot feather also had a small C/P (102.8). DOC/C, TDN/N, and TDP/P were 7.6–16.8, 5.5–22.6, and 22.9–45.6 %, respectively. Except C/N in emergent and riparian species, C/N in the other species and C/P in all the species were lower in their DOM than in the ground leaves. DOM of the macrophytes had a SUVA₂₅₄ value of 0.83–1.80. The FT-IR and ¹³C NMR spectra indicated that the DOM mainly contained polysaccharides and/or amino acids/proteins. Percent of carbohydrates in the DOM was 37.3–66.5 % and was highest in parrot feather (66.5 %) and crofton weed (61.5 %). DOM of water hyacinth, water lettuce, and sago pondweed may have the greatest content of proteins. Aromaticity of the DOM was from 6.9 % in water lettuce to 17.8 % in oriental pepper. DOM of the macrophytes was also different in polarity and percent of Ar–OH. Distinguished characteristics in quantity and quality of the macrophyte-derived DOM may induce unique environmental consequences in the lake systems.     

Comparison of structural features of water-soluble organic matter from atmospheric aerosols with those of aquatic humic substances

Elemental analysis, Fourier transform infrared coupled to attenuated total reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning-¹³C-nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopies were used to compare the chemical features of water-soluble organic compounds (WSOC) from atmospheric aerosols with those of aquatic humic and fulvic acids. The influence of different meteorological conditions on the structural composition of aerosol WSOC was also evaluated. Prior to the structural characterisation, the WSOC samples were separated into hydrophobic acids and hydrophilic acids fractions by using a XAD-8/XAD-4 isolation procedure. Results showed that WSOC hydrophobic acids are mostly aliphatic (40–62% of total NMR peak area), followed by oxygenated alkyls (15–21%) and carboxylic acid (5.4–13.4%) functional groups. Moreover, the aromatic content of aerosol WSOC samples collected between autumn and winter seasons is higher (∼18–19%) than that of samples collected during warmer periods (∼6–10%). The presence of aromatic signals typical of lignin-derived structures in samples collected during low-temperature conditions highlights the major contribution of wood burning processes in domestic fireplaces into the bulk chemical properties of WSOC from aerosols. According to our investigations, aerosol WSOC hydrophobic acids and aquatic fulvic and humic acids hold similar carbon functional groups; however, they differ in terms of the relative carbon distribution. Elemental analysis indicates that H and N contents of WSOC hydrophobic acids samples surpass those of aquatic fulvic and humic acids. In general, the obtained results suggest that WSOC hydrophobic acids have a higher aliphatic character and a lower degree of oxidation than those of standard fulvic and humic acids. The study here reported suggests that aquatic fulvic and humic acids may not be good models for WSOC from airborne particulate matter.     

Does anthracene affect microbial activities and organic matter decomposition? A comparative study in Pinus halepensis litters from Mediterranean coastal and inland areas

The widespread concern about pollution caused by Polycyclic Aromatic Hydrocarbons (PAHs) raises the question of how they affect soil microbial communities which are potentially involved in the transformation of these pollutants. Using microcosms, we describe the effect of anthracene, a model PAH, on microbial communities inhabiting a Pinus halepensis litter from both coastal (COS) and inland (INL) Mediterranean sites. The microcosms were incubated over 3 months (25 °C, 60% WHC) and the effects of anthracene on microbial activities of both litters were monitored. Different enzyme activities (laccase, cellulase, β-glucosidase and acid phosphatase) and microbial respiration were measured and variations in litter chemical composition over incubation were determined using ¹³C Nuclear Magnetic Resonance (NMR) from both sites. Our results show that lignocellulolytic enzymes increased markedly after a 3-month incubation in COS microcosms, especially in the presence of anthracene, whereas INL microcosms were not similarly affected. These results show that anthracene not only has no toxic effect on the microbial activities tested but actually enhances the lignocellulolytic activities of the fungal communities from coastal litters, demonstrating the detoxification potential and resistance of stressed Mediterranean coastal ecosystems.     

A predictive model for copper partitioning to suspended particulate matter in river waters

A chemical equilibrium-based predictive model expressing Cu partitioning as a function of aqueous and solid phase characteristics was developed. The model takes into account only the most important factors that govern Cu partitioning, and therefore results in a relatively simple formulation. It assumes particulate organic carbon (POC) and dissolved organic carbon (DOC) binding sites play the most important role in solid and aqueous phases. The model formulation assumed one-surface site and two dissolved organic matter (DOM) sites, and included the "solids effect". Proton effects were considered for both the particle surface sites and the DOM. The model was calibrated with data for samples collected from the Susquehanna River, and validated with White Clay Creek and Delaware River samples. Copper partitioning in natural water systems with different pH, and concentrations of alkalinity, DOC, POC, total suspended solids (TSS), and total copper was predicted reasonably well.